The oil leakage and discharge of organic pollutants such as phenols have caused serious harm to water environment and human health. The development of technologies that can simultaneously separate oil-water mixtures (especially emulsified oil-water mixtures) and degrade phenols and other organic pollutants is the research focus of oil-water separation membrane or catalytic membrane in future. In this paper, the polyethersulfone (PES) membrane with sponge-like pore structure, high water flux and good compressive resistance was prepared by the phase inversion method with dual-bath coagulation. The 4A-Fe/PES membrane was prepared by co-deposition of PDA/PEI on the membrane surface and subsequent loading of iron species catalyst (4A-Fe) particles. The oil-water separation performance and phenol degradation performance of 4A-Fe/PES membrane were investigated. The results showed that 4A-Fe/PES had good hydrophilicity, oil resistance adhesion and excellent underwater superhydrophobicity. In addition, the degradation of phenol in the oil-water emulsion was realized while dynamically separating the oil-water emulsion. At pH 2, the conversion of phenol reached 98.4% after 50 min, and the separation efficiency of oil-water emulsion reached 99.8%. The separation efficiency of the membrane maintained 94.2% after repeated use for three times.