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|Exhibit 32.1
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|CERTIFICATION PURSUANT TO18 U.S.C. SECTION 1350,AS ADOPTED PURSUANT TOSECTION 906 OF THE SARBANES-OXLEY ACT OF 2002
In
connection with the Quarterly Report on Form 10-Q of Alliance Financial Corporation (the Company)
for the quarter ended September 30, 2007 as filed with the Securities and Exchange Commission on
the date hereof (the Report), I, Jack H. Webb, Chairman of the Board of Directors, President
and Chief Executive Officer of the Company, certify, pursuant to 18 U.S.C. Section 1350, as adopted
pursuant to Section 906 of the Sarbanes-Oxley Act of 2002, that to the best of my knowledge:
(1)           The
Report fully complies with the requirements of Section 13(a) or 15(d) of the Securities Exchange Act of 1934, as amended; and
(2)           The
information contained in the Report fairly presents, in all material respects, the financial condition and results of operations of the Company.

|                        |                                                                              
|----------------------- | -----------------------------------------------------------------------------
|Dated: November 9, 2007 |                                                                              
|                        |                                                                              
|                        | /s/ Jack H. Webb                                                             
|                        |                                                                              
|                        | Name: Jack H. Webb                                                           
|                        | Title: Chairman of the Board, President and Chief Executive           Officer

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