Three-dimensional (3D) architecture of TiO2 hollow sphere has many excellent and interesting performances that attract significant attention nowadays. In this paper, a simple surface erosion approach to the fabrication of TiO2 hollow spheres via the hydrothermal process has been developed. The morphologies and the phase were characterized by scanning electron microscopy (SEM) and X-ray diffractometer (XRD). The results indicate that the anatase-type TiO2 hollow spheres with a diameter of similar to 1 mu m are successfully synthesized. The shell thickness of TiO2 hollow spheres is similar to 150 nm and the size of hollow cavity is similar to 600 nm. By the control experiments, the influence of ammonium fluoride and hydrogen peroxide on the hollow spherical structures was studied. Hydrogen peroxide acts as both the oxidant and the bubble generator, ammonium fluoride is crucial for the erosion and dissolution of titanium, the detailed dissolution-crystallization mechanism for the formation of TiO2 hollow spheres was also proposed. (C) 2009 Elsevier B. V. All rights reserved.