The persistent efforts have been paid to shift the ultraviolet of titania to visible-light-driven photocatalysis. In this work, we explored a facile, cost-effective method to in situ create C-doped hollow TiO2 spheres. This method involved the preparation of monodisperse cationic polystyrene spheres (CPS), sequential deposition of TiO2 precursor via template-directed self-assembly, and the removal of CPS template by calcination at 450 degrees C. The structure and properties of hollow TiO2 catalysts were characterized by N-2 desorption-adsorption, X-ray diffraction (XRD), UV-vis spectroscopy, and X-ray photoelectron spectroscopy (XPS). Results confirmed the carbon doping in the as-prepared hollow TiO2 lattice. When C-doped hollow TiO2 spheres were used as photocatalysts for the degradation of Rhodamine B under visible-light irradiation, the as-synthesized hollow anatase exhibited a superior photocatalytic activity than the commercial P25 and many TiO2-based photocatalysts reported in literature, significantly broadening its potential for many practical applications. (C) 2014 Elsevier B.V. All rights reserved.