<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 31,1999

                                        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. [ ]

The aggregate market value of the voting stock held by non-affiliates of the
registrant as of March 17, 2000 was $21,895,331 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, 1999 are incorporated by reference into Part II.

   Portions of the proxy statement for the annual shareholders meeting to be
       held April 18, 2000, are incorporated by reference into Part III.

         Total number of pages, including cover page and exhibits - 65
<PAGE>

                        FIRST CENTURY BANKSHARES, INC.
                         1999 FORM 10-K ANNUAL REPORT
                               TABLE OF CONTENTS

                                    PART I
<TABLE>
<CAPTION>

<S>                                                                     <C>
        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

<CAPTION>
                                    PART II
<S>                                                                   <C>
        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 8.  FINANCIAL STATEMENTS AND SUPPLEMENTARY DATA........  6
        ITEM 9.  CHANGES IN AND DISAGREEMENTS WITH ACCOUNTANTS ON
                 ACCOUNTING AND FINANCIAL DISCLOSURE................  6
<CAPTION>

                                    PART III

<S>                                                                     <C>
        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

<CAPTION>
                                    PART IV
<S>                                                                     <C>

        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 1999 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 the second quarter of 1999, FCBNA completed the acquisition of the
Hinton, West Virginia branch of City National Bank of West Virginia, Charleston,
West Virginia.  This banking office had approximately $60 million in deposits
and was a natural market extension for the bank.

   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, 1999,
FCBNA had 161 full-time employees and 14 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 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.

                                       3
<PAGE>

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 17 of the accompanying 1999 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.

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, 1999.


                                    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.  Management does not expect that a more active trading market will
develop in the near future for the common stock of the Registrant.

   Page 15 of the 1999 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 17 of the Registrant's 1999 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 17 of the accompanying 1999 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 8.  FINANCIAL STATEMENTS AND SUPPLEMENTARY DATA

   The following financial statements and report of independent accountants for
the years ended December 31, 1999, 1998, and 1997, which are included in the
Corporation's 1999 Annual Report to Stockholders (Exhibit 13), are incorporated
herein by reference:

   The report of independent accountants on page 41 of the Registrant's 1999
Annual Report to Stockholders reflects an unqualified opinion on the 1999 and
1998 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,
1999, issued by PricewaterhouseCoopers, LLP, Charlotte, North Carolina, the
Registrant's independent accountant for those years.

                                                     Reference to
                                                  1999 Annual Report
                                                  ------------------
Consolidated Statements of Financial Condition          Page 18
Consolidated Statements of Income
  and Comprehensive Income                              Page 19
Consolidated Statements of Cash Flows                   Page 20
Consolidated Statements of Changes
  in Stockholders' Equity                               Page 21
Notes to Consolidated Financial
  Statements                                       Pages 22 through 40
Report of Independent Accountants                       Page 41


   The supplementary financial information required by this item is set forth in
Note 17 of "Notes to Consolidated Financial Statements" on Page 39 of the
Corporation's 1999 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.


                                    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 27, 2000 (which is not later than 120 days after December 31, 1999,
the close of the fiscal year of Registrant): and such information is
incorporated herein by reference to such proxy statement.

                                       6
<PAGE>

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 27, 2000, (which is not later than 120 days after
December 31, 1999, 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 27, 2000,
(which is not later than 120 days after December 31, 1999, 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 27, 2000, (which is not later
than 120 days after December 31, 1999, 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.
      No Reports on Form 8-K were filed during the fourth quarter of 1999.

(c)  Exhibits

   3.  Articles of incorporation and bylaws.

       Articles of amendment to articles of incorporation and restated articles
       of incorporation changing the name of the Corporation from Pocahontas
       Bankshares Corporation to First Century Bankshares, Inc. (Bylaws were
       previously filed in a Registration Statement on Form S-14, Registration
       No. 2-85126, and are incorporated herein by reference.)

   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.

                                       7
<PAGE>

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

   27.  Financial Data Schedule

                                       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 23, 2000
                    -------------------------------

  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.

BY:       /s/ B. L. Jackson                            Date: March 21, 2000
   ---------------------------------------------------       --------------
B. L. Jackson, Jr., Chairman of the Board and Director


BY:      /s/ R. W. Wilkinson                           Date: March 21, 2000
   ---------------------------------------------------       --------------
R. W. Wilkinson, President & Chief Executive Officer & Director
 (Principal Executive Officer)


BY:      /s/ Charles A. Peters                         Date: March 21, 2000
   ---------------------------------------------------       --------------
Charles A. Peters, Secretary and Director


BY:      /s/ Paul Cole, Jr.                            Date: March 21, 2000
   ---------------------------------------------------       --------------
Paul Cole, Jr., Director


BY:      /s/ Eustace Frederick                         Date: March 21, 2000
   ---------------------------------------------------       --------------
Eustace Frederick, Director


BY:                                                    Date:
   ---------------------------------------------------       --------------
Robert M. Jones, Jr., M.D., Director


BY:                                                    Date:
   ---------------------------------------------------       --------------
Harold L. Miller, Jr., Director


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


BY:       /s/ Byron K. Satterfield                     Date: March 21, 2000
   ---------------------------------------------------       --------------
Byron K. Satterfield, Director

                                       9
<PAGE>

BY:      /s/ John H. Shott                             Date: March 21, 2000
   ---------------------------------------------------       --------------
John H. Shott, Director


BY:      /s/ Scott H. Shott                            Date: March 21, 2000
   ---------------------------------------------------       --------------
Scott H. Shott, Director


BY:     /s/ Walter L. Sowers                           Date: March 21, 2000
   ---------------------------------------------------       --------------
Walter L. Sowers, Director


BY:     /s/ J. Brookins Taylor, M. D.                  Date: March 21, 2000
   ---------------------------------------------------       --------------
J. Brookins Taylor, M. D., Director


BY:      /s/ Frank W. Wilkinson                        Date: March 21, 2000
   ---------------------------------------------------       --------------
Frank W. Wilkinson, Director

                                       10