A novel catalyst Nb2O5/TiO2 with hierarchical structure was prepared using rape pollen as template, which exhibited good activity in oxidation of alcohols under photo irradiation. The reactions can be carried out under solvent-free conditions with O2 as oxidant and TEMPO (2,2,6,6-Tetramethyl-1-piperidinyloxy) as co-catalyst. The entire reaction process is green and environmentally friendly .The results show that 31 mmol benzaldehyde could be obtained from 10 mL benzyl alcohol. 33% of yield and 98% of selectivity were achieved in this catalytic system. Due to the hierarchical structure and existence of Nb2O5, selectivity improvement was achieved compared with that of bare TiO2.