With the rapid industrial development worldwide, the volume of oily wastewater, including petroleum spills and industrial e uents, has increased dramatically, posing a threat to ecosystems and human health. Membrane separation technology, known for its advantages of phase-transition-free operation, low energy consumption, and simplicity, has gained rapid popularity in wastewater treatment. This study focused on modifying PVDF membranes using PVA-TA hydrogels with two distinct coordination strategies: TA-Fe 3+ coordination and APTMS covalent cross-linking. The resulting composite membranes exhibited superhydrophilic/underwater superoleophobic properties with high emulsion ux (3800-6900 and 4200-12000 Lm − 2 h − 1 bar − 1 ) and separation e ciency (> 98.9% and > 99.3%) for various oil-water emulsions. Notably, the stability of the hydrogel network allowed the composite membranes to maintain elevated uxes (6847.2 and 10266.7 Lm − 2 h − 1 bar − 1 ) and separation e ciencies (97.8% and 99.3%) even after 10 cycles for dichloroethylene-water emulsion. The addition of Fe 3+ and APTMS enhances hydrogel stability and roughness, with APTMS contributing to superior wetting and separation performance. This work provides valuable insights into the impact of different coordination mechanisms on hydrogel-coated membranes, offering a foundation for the development of advanced materials in e cient oil-water separation.