A new heterogeneous PVDF/Fe3+-TiO2 catalytic membrane is prepared by sol-gel method, which had a well catalytic activity to decompose H2O2. The effect of initial pH, e initial concentration of H2O2 and Orange IV, temperature, and membrane area on the reaction rate is discussed. The PVDF/Fe3+-TiO2 catalytic membrane can effectively decolorize Orange IV in the pH range of 3.0-5.0. The optimal concentration of H2O2 is 15mmol/L. The reaction rate constant is proportional to the initial concentrations of Orange IV. The higher the temperature, the faster the reaction rate is, this reaction follows pseudo-first-order kinetics with activation energy of 1.54kJ/mol. Reuse of catalyst did not decrease the removal rate of Orange IV. The experiments of t-butanol, EDTA and XPS measurement showed that •OH, the electron hole and the ferryl are all the reactive species in the degradation of Orange IV.