Through density functional calculations, the Brønsted acidities on various nanostructural ZSM-5 zeolite surfaces were studied as well as the hydrogen exchanging processes with adsorbed H(2)O monomer or dimer. The Brønsted acidities on the four nanostructural surfaces show differences, although slightly, with their strengths increasing as (100) < (210) < (410) < (001). For hydrogen exchanging processes with H(2)O monomer or dimer, the reaction rate increases in the order (210) < (100) < (001) < (410) or (210) < (410) < (001). No transition-state structure is present on H(2)O dimer/(100) surface system. The introduction of a second H(2)O molecule accelerates the hydrogen exchanging processes and meanwhile influences the nanostructural geometries such that they are more evident. Besides the activation barrier, the adsorption energy and reaction heat display differences from one surface to another, which results in the preference of catalytic reactions to a specific nanostructural zeolite surface, such as the hydrogen exchanging processes studied in this paper.