In this study, the TiO2/fly-ash cenospheres were prepared via sol-gel method, and the surface of TiO2/fly-ash cenospheres was further modified by hydrogen peroxide (H2O2). Scanning electron microscopy (SEM), X-ray diffraction (XRD), UV-vis diffuse reflectance spectra (UV-vis DRS), photoluminescence (PL) and X-ray photoelectron spectroscopy (XPS) were applied to characterize structure, performance and chemical composition of as-prepared samples. The photocatalytic activity of as-prepared samples was evaluated by degradation of methylene blue under visible light irradiation. The results indicate that the modified phototcatalyst of TiO2/fly-ash cenospheres is effectively improved the absorption of light. The photocatalytic degradation of methylene blue is enhanced under visible light irradiation, which the degradation rate is higher 42.5% than the untreated TiO2/fly-ash cenospheres with H2O2. Moreover, the simple way to modified TiO2/fly-ash cenospheres and enhancing the photocatalytic activity is better for practical application. (C) 2010 Elsevier B.V. All rights reserved.