In the present work, V2O5 microspheres with the diameters ranging from 1 to 2 mu m are prepared by a facile hydrothermal progress, and then V2O5@TiO2 core-shell microspheres are successfully synthesized by a solution method. It is found that the light absorption intensity of V2O5@ TiO2 core-shell microspheres is greatly enhanced compared with those of V2O5 microspheres and P25 in UV and visible light ranges. The photodegradation rate towards gaseous benzene of V2O5@ TiO2-20% core-shell microspheres is the best one, and it will increase from 27.8% and 10% (pure V2O5 microspheres) to be 100% and 71.8% after 75 min' irradiation under UV and visible light irradiation, respectively. The reason lies in the fact that the formation of V2O5@ TiO2 core-shell microspheres may favor for the light absorption as well as the effective separation of the photoexcited electrons and holes.