A series of poly-o-phenylenediamine/TiO2/fly-ash cenospheres(POPD/TiO2/fly-ash cenospheres) composites have been prepared from o-phenylenediamine and TiO2/fly-ash cenospheres under various polymerization conditions. The properties of the samples were characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), specific surface area (BET), X-ray diffraction (XRD), Fourier transform infrared (FT-IR) and UV-vis diffuse reflectance spectrum (UV-vis DRS). Photocatalytic activity was studied by degradation of antibiotics waste water under visible light. The results indicate that the photo-induced method is viable for preparing modified photocatalysts, and the modified photocatalysts have good absorption in visible light range. The photocatalysts of POPD/TiO2/fly-ash cenospheres which have good performance are prepared at pH 3 and 4, and the polymerized time around 40 min. When the photocatalysts are prepared under the conditions of pH 3 and polymerized time 40 min, the degradation rate of roxithromycin waste water could reach near 60%, and it indicates that the way of POPD modified TiO2/fly-ash cenospheres to degrade the antibiotics waste water is viable. (C) 2009 Elsevier B. V. All rights reserved.