V-MCM-41 molecular sieve with high vanadium content has been prepared by the atrane route. Gas phase partial oxidation of toluene to benzaldehyde on the V-MCM-41 molecular sieves catalysts was studied. The structure and characteristic of catalyst were characterized by means of XRD, UV-vis and so on. The experimental results showed that the vanadium content in the framework related to mole ratio of silica to vanadium. The vanadium content in the framework was the highest, when the mole ratio of Si to V was 30. And the vanadium in the framework may be active centers of catalytic oxidation of toluene to benzaldehyde. Under the condition of atmospheric pressure, mole ratio of Si to V 30, space velocity 800 h-1, n(air):n(toluene)=5 and reaction temperature 450°C，the conversion of toluene, selectivity to benzaldehyde and its yield were 20.8%, 41.8% and 8.7% respectively.