Fluorinated TiO2 hollow microspheres with three-dimensional hierarchical architecture were prepared by solvothermally treatment using solid microspheres as precursor. The obtained solid and hollow TiO2 microspheres were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET), X-ray photoelectron spectroscopy (XPS), UV-Vis diffuse reflectance spectrum (DRS) and photoluminescence (PL) spectra. The photocatalytic activity of as-prepared solid and hollow TiO2 microspheres was determined by degradation of methyl orange (MO) under visible light irradiation. The results showed that the surface fluorination, the existence of accessible mesopores channels, and the increased light harvesting abilities could remarkably improve the photocatalytic activity of TiO2 hollow microspheres. (C) 2011 Elsevier B.V. All rights reserved.