Visible-light-sensitive vanadium-doped TiO 2 hollow microspheres were prepared by a novel one-step template method. The novel catalysts showed pure anatase phase and better spherical morphology, compared with that of the traditional samples. The possible formation mechanism of TiO 2 hollow microspheres prepared by the novel method has been proposed. The samples fabricated by the novel method not only exhibited the superior photocatalytic activity for the decomposition of methylene blue under visible-light irradiation, but also can be readily recovered from the solution by filtration after the photocatalysis.