Mesoporous TiO2 hollow spheres were prepared in a solvothermal process, which did not involve any templates and surfactants. Meanwhile, the photocatalytic activity of TiO2 hollow spheres was studied using methyl orange as a probe. The results indicate that the anatase TiO2 hollow spheres with mesoporous walls and high specific surface area (141 m(2) g(-1)) can be obtained using this simple method. The mean diameter and wall thickness of spheres are about 700 nm and 90 nm, respectively. Moreover, the as-prepared TiO2 hollow spheres display high photocatalytic activity with 98% of degradation ratio of methyl orange after 30 min irradiation. (C) 2012 Elsevier Ltd. All rights reserved.