Fluoropolymer poly-vinylidene-fluoride modified TiO2 (PVDF/TiO2) were prepared via a simple chemisorption approach and characterized by thermo gravimetric analyse, transmission electron microscope, X-ray diffraction, X-ray photoelectron spectroscopy and photoluminescence spectra. The modified mechanism and the photocatalytic selectivity of the PVDF/TiO2 were studied. The existence of Ti-F coordination bond on the interface between TiO2 and PVDF was confirmed. For the PVDF modification, the photocatalytic degradation (PCD) of cationic dye was greatly enhanced, and the PCD of anionic dye was obviously inhibited. PVDF/TiO2 shows high photocatalytic selectivity than that of TiO2 by degrading mixed solution of cationic dyes MB and anionic dyes MO. The selectivity can be tuned by changing the PVDF modification amount. Crown Copyright (C) 2011 Published by Elsevier B.V. All rights reserved.