Notable strides have been made in membrane technology, yet challenges persist in separating complex oily wastewater. Thus, developing an advanced, high-flux filtration membrane that resists oil and degrades organic pollutants is vital. Herein, we developed a novel TiO2-MX@PVDF ESM with unique cauliflower-like structures, imparting superwetting behaviour for effective water capture and oil droplet repulsion, thereby improving oil/water separation. Additionally, it exhibits excellent oil-fouling resistance despite multiple separation cycles. Furthermore, its light-trapping ability and unique band structure degrade the malachite green dye. Thus, this work introducesan achievable approach for designing dual-functional membranes to address challenging oily wastewater.