12-Molybdophosphoric acid (MPA) supported on V2O5 dispersed γ-Al2O3 catalysts with different loadings were prepared and characterized by BET surface area, X-ray diffraction, FT-infrared, laser Raman, X-ray photoelectron spectroscopy and temperature programmed reduction techniques. The catalytic activities were evaluated for the aerobic oxidation of benzyl alcohol. The conversion of benzyl alcohol increased with the amount of MPA content and the catalyst with 15 wt% of MPA showed highest activity. The synergistic effect of V2O5 and MPA was observed for the oxidation of benzyl alcohol compared to MPA on alumina without V2O5. The XPS results suggest the participation of both Mo and V in the reaction as the used catalysts showed the reduced oxidation states of both Mo and V. The high selectivity of the catalysts is due to the presence of V2O5, which induces the redox nature to the catalyst and also preventing the decomposition of MPA on Al2O3.