Developing a strong catalytic antifouling membrane to achieve efficient sewage purification has great potential for alleviating water crisis. In this work, we designed and prepared an Fe/Cu-layered double hydroxide (Fe-Cu LDH)-coated polyvinylidene fluoride (PVDF) composite membrane (PVDF/Fe-Cu LDHs) with strong antifouling and activating peroxymonosulfate (PMS) catalytic degradation performance through polydopamine-coordination anchoring and hydrothermal reaction. The results showed that abundant hydroxyl groups of the LDH surface endowed the superhydrophilicity (water contact angle <10°) and underwater superoleophobicity (underwater-oil contact angle >150°) of the membrane surface, which displayed outstanding resistance to crude oil adhesion. With assistance of the LDH surface-bound sulfate radical of the peroxymonosulfate system, the PVDF/Fe-Cu LDH membrane demonstrated robust catalytic degradation performance for the methylene blue (MB) in the dark; the degradation rate constant (k, min-1) reached 0.96. Meanwhile, facing the oily wastewater, the selective wettability and charge effect of LDH of the surface made the PVDF/Fe-Cu LDH membrane realize the separation for the various surfactant-free and surfactant-stabilized emulsions. Importantly, the PMS-activation catalytic produced the ROS (•SO4-,•OH, •O2-, and 1O2), which enhanced the regeneration of the fouled PVDF/Fe-Cu LDH membrane and obtained a high flux recovery ratio in the dark (94.7%) after 10 cycles of separation experiments. Hence, we believed that the PVDF/Fe-Cu LDH membrane can provide inspiration for the development and further practical application of antifouling membranes.