A new kind of PVDF/Fe3+/Cu2+ catalytic membrane was prepared and used as a heterogeneous Fenton-like catalyst to degrade Orange IV in the presence of H2O2. The effect of initial concentration of H2O2 and Orange IV, initial pH, reaction temperature and catalyst dosage on the reaction rate was studied. The results show that the higher the concentration of H2O2, the faster the reaction rate is. The reaction rate increased with the increase of temperature with the activation energy 30.18KJ•mol-1. The PVDF/Fe3+/Cu2+ catalytic membrane can effectively decolorize Orange IV in the pH range of 3.1-5.3. The decolorization rate of Orange IV decreased with the increase of initial concentration of Orange IV. The decolorization rate of Orange IV increased with the increase of dosage of catalyst. The reactive intermediates for this reaction is HO• based on t-butanol experiments.