Bi-doped hollow titania spheres were prepared using carbon spheres as template and Bi-doped titania nanoparticles as building blocks. The Bi-doped titania nanoparticles were synthesized at low temperature. The prepared hollow spheres were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), UV-vis diffuse reflectance spectrum (DRS) and X-ray photoelectron spectroscopy (XPS). The effects of Bi content on the physical structure and photocatalytic activity of doped hollow titania sphere samples were investigated. Results showed that there was an optimal Bi-doped content (4%) for the photocatalytic degradation of methylene blue (MB). (C) 2011 Elsevier B. V. All rights reserved.