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A new kind of Fe3+/polyvinylidene fluoride membrane (PVDF)-poly methyl methacrylate (PMMA) asymmetric catalytic membrane was prepared by the blending method. The hydrophilicity and anti-fouling properties of Fe3+/PVDF catalytic membrane was increased significantly after blended with PMMA. The influence of some factors such as polymer blending ratio, polymer concentration, additives, temperature of coagulation bath on the pure water flux and BSA retention were discussed. The catalytic activity of Fe3+/PVDF-PMMA catalytic membrane was evaluated by the degradation of refractory dye Orange IV in the presence of H2O2. The results showed that the addition- of appropriate PMMA in the preparation of Fe3+/PVDF membrane has greatly decreased the contact angle of the membrane. Fe3+/PVDF-PMMA membrane had better anti-fouling than Fe3+/PVDF membrane. The Fe3+/PVDF-PMMA catalytic membranes retention rate decreased and pure water flux increased with the increase of PMMA. When the mass ratio of (PVDF) / (PMMA) was 7:3 and the additive was poly (ethylene glycol) (PEG600), the properties of this membrane were better. This kind of Fe3+/PVDF-PMMA catalytic membrane has not only good filtration efficiency but also good catalytic activity to effectively decompose Orange IV.