The surface molecular imprinted photocatalyst of poly-o-phenylenediamine (POPD) modified TiO2/fly-ash cenospheres was prepared by molecular imprinted technology with ciprofloxacin (CIP), ethylene glycol dimethacrylate (EGDMA) and acrylamide as the molecular template, cross-linking agent and functional monomer, respectively. The imprinted photocatalysts were further characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), specific surface area, UV-vis diffuse reflectance spectra (UV-vis DRS) and Fourier transform infrared (FT-IR). The preferential selection and activity of imprinted photocatalysts were evaluated by degradation of antibiotic waste water. The results indicate that the surface imprinted photocatalysts could effectively prefer degradation of molecular template and enhance the photocatalytic activity. The imprinted photocatalysts showed higher selection of adsorption and photo-degradation on the molecular template (ciprofloxacin) than non-molecular template. The degradation rate of molecular template could reach 70% in 60 min under visible light irradiation. The degradation intermediate product of ciprofloxacin was further discussed. (C) 2012 Elsevier B.V. All rights reserved.