<PAGE>

               UNITED STATES SECURITIES AND EXCHANGE COMMISSION
                           Washington, D. C., 20549
                                   FORM 10-K

     [X] Annual Report Pursuant to Section 13 or 15 (d) of the Securities
                             Exchange Act of 1934
                  For the fiscal year ended December 31, 2000

                                      OR

     [_] Transition Report Pursuant to Section 13 or 15 (d) or the Securities
                             Exchange Act of 1934
                For the transition period from ___________ to __________

                        Commission file number: 0-11671


                        FIRST CENTURY BANKSHARES, INC.
                        ------------------------------
             (Exact name of registrant as specified in its charter)

            West Virginia                                     55-0628089
            -------------                                     ----------
    (State or other jurisdiction of                         (IRS Employer
  incorporation or organization)                         Identification No.)

     500 Federal Street, Bluefield, WV                          24701
     ---------------------------------                          -----
  (Address of principal executive offices)                    (Zip Code)

    Registrant's telephone number, including area code:     (304) 325-8181
                                                             -------------

          Securities registered pursuant to Section 12(b) of the Act:

                                                        Name of each exchange on
            Title of each class                             which registered
            -------------------                           ----------------------
                  NONE                                            NONE

          Securities registered pursuant to Section 12(g) of the Act:

        First Century Bankshares, Inc.: $1.25 Par Value - Common Stock
                               (Title of class)

 Indicate by check mark whether the registrant (1) has filed all reports
  required to be filed by Section 13 or 15 (d) of the Securities Exchange Act of
  1934 during the preceding 12 months (or for such shorter period that the
  registrant was required to file such reports), and (2) has been subject to
        such filing requirements for the past 90 days. Yes [X] No [_]

 Indicate by check mark if disclosure of delinquent filers pursuant to Item 405
  of Regulation S-K is not contained herein, and will not be contained, to the
  best of registrant's knowledge, in definitive proxy or information statements
    incorporated by reference in Part III of this Form 10-K or any amendment
                           to this Form 10-K. [X]

  The aggregate market value of the voting stock held by non-affiliates of the
    registrant as of March 16, 2001 was $19,410,090 and the number of shares
          outstanding of the registrant's common stock was 2,000,000


                     DOCUMENTS INCORPORATED BY REFERENCE.
     Portions of the annual shareholders report for the fiscal year ended
         December 31, 2000 are incorporated by reference into Part II.

                Portions of the proxy statement for the annual
                shareholders meeting to be held April 17, 2001,
                 are incorporated by reference into Part III.

         Total number of pages, including cover page and exhibits - 64
<PAGE>

                        FIRST CENTURY BANKSHARES, INC.
                         2000 FORM 10-K ANNUAL REPORT
                               TABLE OF CONTENTS

<TABLE>
               <S>                                                                               <C>
                                                       PART I

               ITEM 1.  BUSINESS..............................................................         3
               ITEM 2.  PROPERTIES............................................................         5
               ITEM 3.  LEGAL PROCEEDINGS.....................................................         5
               ITEM 4.  SUBMISSION OF MATTERS TO A VOTE OF SECURITY HOLDERS...................         5

                                                        PART II
               ITEM 5.  MARKET FOR REGISTRANT'S COMMON EQUITY AND RELATED
                    STOCKHOLDER MATTERS.......................................................         5
               ITEM 6.  SELECTED FINANCIAL DATA...............................................         6
               ITEM 7.  MANAGEMENT'S DISCUSSION AND ANALYSIS OF FINANCIAL
                    CONDITION AND RESULTS OF OPERATIONS.......................................         6
               ITEM 7A. QUANTITATIVE  AND QUALITATIVE DISCLOSURES
                    ABOUT MARKET RISK.........................................................         6
               ITEM 8.  FINANCIAL STATEMENTS AND SUPPLEMENTARY DATA...........................         6
               ITEM 9.  CHANGES IN AND DISAGREEMENTS WITH ACCOUNTANTS ON
                    ACCOUNTING AND FINANCIAL DISCLOSURE.......................................         6

                                                       PART III

               ITEM 10.  DIRECTORS AND EXECUTIVE OFFICERS OF THE REGISTRANT...................         6
               ITEM 11.  EXECUTIVE COMPENSATION...............................................         7
               ITEM 12.  SECURITY OWNERSHIP OF CERTAIN BENEFICIAL OWNERS
                    AND MANAGEMENT............................................................         7
               ITEM 13.  CERTAIN RELATIONSHIPS AND RELATED TRANSACTIONS.......................         7

                                                        PART IV

               ITEM 14.  EXHIBITS, FINANCIAL STATEMENT SCHEDULES,
                    AND REPORTS ON FORM 8-K...................................................     7 - 8
               SIGNATURES.....................................................................    9 - 10
</TABLE>

                                       2
<PAGE>

                                    PART I
ITEM 1.  BUSINESS

FIRST CENTURY BANKSHARES, INC.

      First Century Bankshares, Inc. ("Corporation" or "Registrant"), formerly
Pocahontas Bankshares Corporation, was organized under the laws of West Virginia
in 1983 at the direction of the Board of Directors of The First National Bank of
Bluefield ("Bluefield"). On March 1, 1984, the effective date of the corporate
reorganization, the shareholders of Bluefield became the shareholders of the
Corporation, and Bluefield became a wholly-owned subsidiary of the Corporation.
On March 11, 1988, the Registrant acquired control of the Bank of Oceana,
Oceana, WV ("Oceana"). On May 24, 1991, the Registrant formed First Century
Bank, Roanoke, Virginia. During 1993, the main office of First Century Bank was
redesignated to Wytheville, Virginia. Effective November 28, 1994, the merger of
Bank of Oceana into The First National Bank of Bluefield was completed and the
name of the resulting entity was changed to First Century Bank, National
Association ("FCBNA"), with its main office in Bluefield, West Virginia.
Effective May 7, 1999, First Century Bank was merged into FCBNA. Substantially,
all of the operations of the Corporation are carried on through FCBNA which is
the Registrant's only subsidiary. The officers and directors of the Corporation,
who are also officers and directors of FCBNA, receive their entire compensation
from FCBNA. The Corporation's executive offices are located at 500 Federal
Street, Bluefield, West Virginia.

      The Registrant's principal business and major source of revenue is, and is
expected to remain, commercial banking. The Registrant currently derives
substantially all its revenues from dividends paid by the subsidiary bank. The
earnings, asset growth and current capital position of the subsidiary influence
dividend payments by FCBNA. In addition, various regulatory agencies control the
payment of dividends. For additional information regarding the payment of
dividends, see Note 16 of the Notes to the Consolidated Financial Statements in
the Registrant's 2000 Annual Report to the Stockholders attached as Exhibit 13
to this report.

FIRST CENTURY BANK, N.A.

      First Century Bank, N.A., a national banking association, was organized
and chartered in 1891 as The First National Bank of Bluefield, under the laws of
the State of West Virginia and the National Bank Act. FCBNA offers customary
banking services, including commercial, real estate, installment, and other
loans; interest-bearing and non-interest bearing transaction accounts, savings
and time deposit accounts including certificates and other deposit accounts,
featuring various maturities and market rates; Individual Retirement Accounts;
Visa and MasterCard services under an arrangement with a correspondent bank;
safe deposit facilities; personal and corporate trust services; and various cash
management services.

      During 2000, management made commitments to expand nontraditional
financial services offered to the Corporation's customers. The Corporation
entered into an affiliation arrangement with Salomon Smith Barney, Inc. to
provide full service brokerage services. Additionally, the Corporation entered
into an affiliation with the Banker's Insurance Corporation, a relationship with
67 community banks, which will offer a full range of insurance products and
services.

      In addition to the main office, FCBNA currently operates nine additional
branches in Mercer, Summers and Wyoming counties in southern West Virginia and
Tazewell and Wythe Counties in southwestern Virginia. As of December 31, 2000,
FCBNA had 163 full-time employees and 15 part-time employees. FCBNA is not a
party to any collective bargaining agreements, and, in the opinion of
management, enjoys satisfactory relations with its employees.

COMPETITION

      Vigorous and intense competition exists in all areas where the Registrant
and its subsidiary are engaged in business, generally from other banks located
in southern West Virginia and southwestern Virginia. However, this competition
is not only limited to other commercial banks. The subsidiary banks also compete
for certain lines of business with savings and loan associations, mortgage
companies, credit unions, consumer finance companies, leasing companies,
insurance companies, mutual funds and brokerage firms. Significant competition
also exists from state-wide and nation-wide bank holding companies located in
West Virginia and Virginia, which have offices in the communities the Registrant
serves. These institutions are larger in terms of capital, resources and
personnel. This requires that the Registrant place a high emphasis on quality
service, with a significant amount of personal attention, in

                                       3
<PAGE>

order to effectively compete with these larger institutions. Management feels
that this competitive environment will continue in the markets in which the
Registrant currently operates.

FUTURE ACQUISITIONS AND EXPANSION

      The Registrant may from time to time consider expansion of its banking
operations through acquisition of or formation of other banks and/or bank
related businesses. In addition to traditional banking products and services,
with the passage of the Graham-Leach-Bliley Financial Modernization Act, the
registrant will evaluate the potential of offering new financial services
allowed under the Act.

SUPERVISION AND REGULATION

      The Corporation is under the jurisdiction of the United States Securities
and Exchange Commission and the State of West Virginia's Secretary of State with
respect to matters relating to the offer and sale of its securities and matters
relating to reporting to such commissions and to its shareholders.

      The Corporation is a registered holding company under the Bank Holding
Company Act of 1956, as amended, and is regulated by the Federal Reserve. As a
bank holding company, the Corporation is required to file with the Federal
Reserve an Annual Report and such additional information as the Federal Reserve
may require pursuant to the Bank Holding Company Act. The Federal Reserve may
also conduct examinations of the Corporation and each subsidiary. The Bank
Holding Company Act requires every bank holding company to obtain prior approval
from the Federal Reserve before acquiring direct or indirect ownership or
control of more than five percent of the voting shares of any bank which is not
already majority owned or controlled by that bank holding company. Pursuant to
West Virginia law, the Corporation is authorized to acquire ownership or control
of additional banks in the state of West Virginia, provided, this does not
result in control of more than twenty percent (20%) of the total deposits of all
depository institutions in the state of West Virginia. Acquisition of such
additional banks would require approval from the Federal Reserve and the
Commissioner of Banking of the State of West Virginia.

      The Bank Holding Company Act further provides that the Federal Reserve
will not approve any acquisition, merger or consolidation (a) which would result
in a monopoly, (b) which would be in furtherance of any combination or
conspiracy to monopolize or attempt to monopolize the business of banking in any
part of the United States, (c) the effect of which may be to substantially
lessen competition or to tend to create a monopoly in any section of the country
or (d) which in any other manner would be in restraint of trade, unless the
anti-competitive effects of the proposed transaction are clearly outweighed by
the public interest in the probable effect of the transaction meeting the
convenience and needs of the community to be served.

      In addition to having the right to acquire ownership and control of other
banks, the Corporation is authorized to acquire ownership and control of
non-banking companies, provided the activities of such companies are so closely
related to banking or managing or controlling banks that the Federal Reserve
considers such activities to be proper to the operation and control of banks.
Regulation Y, promulgated by the Federal Reserve, sets forth those activities
which are regarded as closely related to banking or managing or controlling
banks and thus are permissible activities for bank holding companies, subject to
the approval by the Federal Reserve in individual cases.

      Subsidiary banks of a bank holding company are subject to certain
restrictions imposed by the Bank Holding Company Act on any extension of credit
to the bank holding company or any of its subsidiaries, on investment in the
stock or other securities thereof, and on the taking of such stock or securities
for loans to any borrower. Further, under Section 106 of the 1970 amendments to
the Bank Holding Company Act and the regulations of the Federal Reserve, a bank
holding company through its banking subsidiaries is prohibited from engaging in
certain tie-in arrangements in connection with any extension of credit or
provision of any property or services. The Federal Reserve possesses cease and
desist powers over bank holding companies and their non-bank subsidiaries if
their actions are unsafe or unsound practices or violations of law.

      FCBNA operates as a national banking association subject to examination by
the Office of the Comptroller of the Currency (the "Comptroller"). The
Comptroller regulates all areas of a national bank's operations, both commercial
and trust, including loans, deposits, mergers, branches and payments of
dividends.

                                       4
<PAGE>

      FCBNA, by means of its national charter, is also a member of the Federal
Reserve System, and as such, is affected by the monetary policies of the Federal
Reserve System, which regulates the national money supply in order to mitigate
recessionary and inflationary pressures. The instruments of monetary policy
employed by the Federal Reserve include open market operations in U. S.
Government securities, changes in the reserve requirement for member banks, and
changes in the discount rate for member bank borrowings.

      In view of the changing conditions in the national economy and the money
markets, as well as, the effect of actions by monetary and fiscal authorities,
including the Federal Reserve, no prediction can be made as to possible future
changes in interest rates, deposit levels, loan demand of the business and
earnings of the Corporation or its subsidiaries.

      FCBNA is also insured and regulated by the Federal Deposit Insurance
Corporation (the "FDIC"). The major function of the FDIC with respect to insured
member banks is to pay depositors to the extent provided by law in the event an
insured bank is closed without adequately providing for payment of the claims of
the depositors.

STATISTICAL DISCLOSURE

      The statistical and other financial data disclosures required pursuant to
Guide 3 of the Preparation and Filing of Reports and Registration Statements
under the Securities Exchange Act of 1934 are contained within Management's
Discussion and Analysis of Financial Condition and Results of Operations
appearing on pages 3 through 19 of the accompanying 2000 Annual Report to
Stockholders, incorporated herein by reference in this Form 10-K annual report
as Exhibit 13.

ITEM 2.  PROPERTIES

      The executive offices of the Registrant are located at 500 Federal Street,
Bluefield, West Virginia. There are ten properties owned or leased by the
subsidiary banks consisting of modern single purpose facilities that house all
the amenities to comfortably conduct the full range of financial services
provided by the Registrant and its subsidiaries. Eight of these offices are
owned and two are leased.

ITEM 3.  LEGAL PROCEEDINGS

      Neither the Registrant nor any of its subsidiaries are presently
involved in any material legal proceedings other than ordinary routine
litigation incidental to its business, except as follows:

      In First Century Bank, National Association, v. Community National Bank,
in the United States District Court, Western District of Virginia, Roanoke
Division, Case No. 7:00CV00904, FCBNA brought suit against the defendant
seeking recovery of approximately $3,400,000 plus interest and costs related
to the dishonor of checks presented for payment by FCBNA as a depository bank
and violations of Regulation CC of The Code of Federal Regulations, Part 229
of Title 12. The defendant has filed third party complaints against additional
parties. While the net recovery cannot be stated with reasonable certainty,
the claims asserted against the defendant are valid and a recovery is
expected.

ITEM 4.  SUBMISSION OF MATTERS TO A VOTE OF SECURITY HOLDERS

There were no matters submitted to security holders for a vote during the fourth
quarter ended December 31, 2000.

                                    PART II


ITEM 5.  MARKET FOR REGISTRANT'S COMMON EQUITY AND RELATED STOCKHOLDER MATTERS

      No established public market presently exists for the common stock of the
Registrant. Quotations may be obtained through the OTC Bulletin Board under the
trading symbol FCBS. Management does not expect that a more active trading
market will develop in the near future for the common stock of the Registrant.

      Page 17 of the 2000 Annual Report to Stockholders (incorporated herein by
reference) describes further the information for market, stockholders, and
dividends. The payment of dividends is subject to the restrictions described in
Note 16 of the Notes to Consolidated Financial Statements. The Board of
Directors evaluates the dividend payment on the Registrant's common stock after
the conclusion of each calendar quarter.

                                       5
<PAGE>

ITEM 6.  SELECTED FINANCIAL DATA

      The selected financial data required by this item is set forth in
Management's Discussion and Analysis of Financial Condition and Results of
Operations on page 19 of the Registrant's 2000 Annual Report to Stockholders
(Exhibit 13), incorporated herein by reference.

ITEM 7.  MANAGEMENT'S DISCUSSION AND ANALYSIS OF FINANCIAL CONDITION AND RESULTS
         OF OPERATIONS

      Management's Discussion and Analysis of Financial Condition and Results of
Operations appearing on pages 3 through 19 of the accompanying 2000 Annual
Report to Stockholders is incorporated by reference in this Form 10-K annual
report as Exhibit 13. Management's discussion and analysis should be read in
conjunction with the related financial statements and notes thereto.

ITEM 7A.  QUANTITATIVE AND QUALITATIVE DISCLOSURES ABOUT MARKET RISK

      Information for this item can be found in the Asset and Liability
Management and Interest Rate Sensitivity section of Management's Discussion and
Analysis of Financial Condition and Results of Operations appearing on pages 12
through 13; and Note 15, Financial Instruments, Concentrations of Credit and
Fair Values, appearing on pages 37 through 38 of the accompanying 2000 Annual
Report to Stockholders, and is incorporated by reference in this Form 10-K

ITEM 8.  FINANCIAL STATEMENTS AND SUPPLEMENTARY DATA

      The following financial statements and report of independent accountants
for the years ended December 31, 2000, 1999, and 1998, which are included in the
Corporation's 2000 Annual Report to Stockholders (Exhibit 13), are incorporated
herein by reference:

      The report of independent accountants on page 42 of the Registrant's 2000
Annual Report to Stockholders reflects an unqualified opinion on the 2000 and
1999 consolidated statements of financial condition and the related consolidated
statements of income and comprehensive income, changes in stockholders' equity,
and cash flows for each of the years in the three-year period ended December 31,
2000, issued by PricewaterhouseCoopers, LLP, Greensboro, North Carolina, the
Registrant's independent accountant for those years.

                                                      Reference to
                                                   2000 Annual Report
                                                   ------------------
Consolidated Statements of Financial Condition           Page 20
Consolidated Statements of Income
  and Comprehensive Income                               Page 21
Consolidated Statements of Cash Flows                    Page 22
Consolidated Statements of Changes
 in Stockholders' Equity                                 Page 23
Notes to Consolidated Financial
 Statements                                        Pages 24 through 41
Report of Independent Accountants                        Page 42


      The supplementary financial information required by this item is set forth
in Note 17 of "Notes to Consolidated Financial Statements" on Page 40 of the
Corporation's 2000 Annual Report to Stockholders (Exhibit 13), incorporated
herein by reference.

ITEM 9.  CHANGES IN AND DISAGREEMENTS WITH ACCOUNTANTS ON ACCOUNTING AND
         FINANCIAL DISCLOSURE

      There have been no disagreements with the independent accountants on
accounting principles or practices, financial statement disclosure, or auditing
scope or procedure.

                                       6
<PAGE>

                                   PART III


ITEM 10.  DIRECTORS AND EXECUTIVE OFFICERS OF THE REGISTRANT

      The information concerning the directors and executive officers of the
Registrant has been omitted in accordance with General Instruction G since
Registrant has filed its definitive proxy statement with the Commission on or
about March 23, 2001 (which is not later than 120 days after December 31, 2000,
the close of the fiscal year of Registrant): and such information is
incorporated herein by reference to such proxy statement.

ITEM 11.  EXECUTIVE COMPENSATION

      Management remuneration has been omitted in accordance with General
Instruction G since Registrant has filed its definitive proxy statement with the
Commission on or about March 23, 2001, (which is not later than 120 days after
December 31, 2000, the close of the fiscal year of Registrant): and such
information is incorporated herein by reference to such proxy statement.

ITEM 12.  SECURITY OWNERSHIP OF CERTAIN BENEFICIAL OWNERS AND MANAGEMENT

      Security ownership of certain beneficial owners and management has been
omitted in accordance with General Instruction G since Registrant has filed its
definitive proxy statement with the Commission on or about March 23, 2001,
(which is not later than 120 days after December 31, 2000, the close of the
fiscal year of Registrant): and such information is incorporated herein by
reference to such proxy statement.

ITEM 13.  CERTAIN RELATIONSHIPS AND RELATED TRANSACTIONS

      Certain relationships and related transactions has been omitted in
accordance with General Instruction G since Registrant has filed its definitive
proxy statement with the commission on or about March 23, 2001, (which is not
later than 120 days after December 31, 2000, the close of the fiscal year of
Registrant): and is incorporated herein by reference to such proxy statement.

                                    PART IV


ITEM 14.  EXHIBITS, FINANCIAL STATEMENT SCHEDULES, AND REPORTS ON FORM 8-K

(a)   1.  Financial Statements.
           See Item 8 on Page 6 of this document for a listing of all Financial
           Statements, Accountants' Report, and Supplementary Data.

      2.  Financial Statement Schedules.
           All schedules are omitted, as the required information is
           inapplicable or the information is presented in the Consolidated
           Financial Statements or related notes.

(b)   Reports on Form 8-K.
           On November 13, 2000, the Corporation filed a current report on Form
           8-K announcing its earnings for the period ended September 30, 2000
           and warned of lower earnings for the year ended December 31, 2000.

(c)   Exhibits

      3.   Articles of incorporation and bylaws.
           Articles of amendment to articles of incorporation and restated
           articles of incorporation were filed with the Annual Report on Form
           10-K for the year ended December 31, 1999 and are incorporated herein
           by reference. (Bylaws were previously filed in a Registration
           Statement on Form S-14, Registration No. 2-85126, and are
           incorporated herein by reference.)

                                       7
<PAGE>

      10.  Material Contracts
           a.     Sample agreement pertaining to a split-dollar life insurance
                  arrangement between FCBNA and Messrs. Wilkinson, Satterfield,
                  Kennett and Albert.

      11.  Statement regarding computation of per share earnings.
           (These statements are included in the notes to the consolidated
           financial statements which are incorporated herein by reference.)

      13.  Annual report to security holders.

      22.  Subsidiaries of the registrant.
           (This disclosure is included in the notes to the consolidated
           financial statements which are incorporated herein by reference.)

                                       8
<PAGE>

                                  SIGNATURES

     Pursuant to the requirements of Section 13 or 15(d) of the Securities
Exchange Act of 1934, the registrant has duly caused this report to be signed on
its behalf by the undersigned, thereunto duly authorized.

     (Registrant)         First Century Bankshares, Inc.

                          BY:   /s/ J. Ronald Hypes
                             --------------------------------------
                          J. Ronald Hypes, Treasurer
                          (Principal Accounting & Financial Officer)

                          DATE:           March 21, 2001
                               ------------------------------------

     Pursuant to the requirements of the Securities Exchange Act of 1934, this
report has been signed below by the following persons on behalf of the
registrant and in the capacities and on the dates indicated.

<TABLE>
<S>                                                                 <C>
BY:      /s/ B. L. Jackson                                          Date:  March 20, 2001
   -----------------------------------------------------------           ---------------------
B. L. Jackson, Jr., Chairman of the Board and Director


BY:      /s/ R. W. Wilkinson                                        Date:  March 20, 2001
   ------------------------------------------------------------          ---------------------
R. W. Wilkinson, President & Chief Executive Officer & Director
   (Principal Executive Officer)


BY:      /s/ Charles A. Peters                                      Date:  March 20, 2001
   ------------------------------------------------------------          ---------------------
Charles A. Peters, Secretary and Director


BY:      /s/ Paul Cole, Jr.                                         Date:  March 20, 2001
   ------------------------------------------------------------          ---------------------
Paul Cole, Jr., Director


BY:                                                                 Date:
   ------------------------------------------------------------          ---------------------
Eustace Frederick, Director


BY:      /s/ Robert M. Jones, Jr.                                   Date:  March 20, 2001
   ------------------------------------------------------------          ---------------------
Robert M. Jones, Jr., M.D., Director


BY:      /s/ Marshall S. Miller                                     Date:  March 20, 2001
   ------------------------------------------------------------          ---------------------
Marshall S. Miller, Director


BY:                                                                 Date:
  -------------------------------------------------------------          ---------------------
C. E. Richner, Director


BY:      /s/ Byron K. Satterfield                                   Date:   March 20, 2001
   ------------------------------------------------------------          ---------------------
Byron K. Satterfield, Director
</TABLE>

                                       9
<PAGE>

<TABLE>
<S>                                                                 <C>
BY:      /s/ John H. Shott,                                         Date:   March 20, 2001
   ---------------------------------------------------------             ---------------------
John H. Shott, Director

BY:      /s/ Scott H. Shott                                         Date:   March 20, 2001
   ---------------------------------------------------------             ---------------------
Scott H. Shott, Director


BY:                                                                 Date:
   ---------------------------------------------------------             ---------------------
Walter L. Sowers, Director


BY:      /s/ J. Brookins Taylor, M. D.                              Date:   March 20, 2001
   ---------------------------------------------------------             ---------------------
J. Brookins Taylor, M. D., Director


BY:      /s/ Frank W. Wilkinson                                     Date:   March 20, 2001
   ---------------------------------------------------------             ---------------------
Frank W. Wilkinson, Director
</TABLE>

                                       10