TiO2 hollow spheres are prepared by a template method, and TiO2@V2O5 core-shell hollow porous microspheres are successfully synthesized through a facile hydrothermal progress followed by sol-gel technique. The diameters of TiO2@V2O5 core-shell hollow porous microspheres are quite uniform ranging from 700 nm to 900 nm. It is found that the photodegradation rate of TiO2@V2O5 core-shell hollow porous microspheres towards benzene is greatly enhanced compared with that of TiO2 hollow porous microspheres and P25, and TiO2@V2O5-10% core-shell hollow porous microspheres possess the best photocatalytic activity of 100% in 55 min and 68.9% in 75 min under UV-visible and visible light irradiation, respectively. The reason lies in the fact that the light absorption range is extended due to the narrowed band gap of TiO2@V2O5 core-shell hollow porous microspheres, and the photogenerated electrons and holes are effectively separated as well as the surface charge carrier transfer rate is promoted.