The cost-effective treatment of emulsified oily wastewater discharged by many industries and human societies is a great challenge. Herein, based on an aliphatic polyketone (PK) polymer with a good membrane formation ability and an intrinsic intermediate hydrophilicity, a new class of reduced PK (rPK) membranes combining an all hydrophilic and electrically neutral surface chemistry comprising ketone and hydroxyl groups, and a fibril-like morphology featuring re-entrant structure, was facilely prepared by phase separation and following fast surface reduction. The synergetic cooperation of surface chemistry and surface geometry endowed the prepared membranes with excellent superhydrophilicity, underwater superoleophobicity, and underoil superhydrophilicity, in addition to antiprotein-adhesion property. Thus, fouling-resistant and self-cleaning filtrations of challenging oil-in-water emulsions containing adhesive oil, surfactant, high salinity, and proteins were effortlessly realized with high flux (up to ∼50 000 L m -2 h -1 bar -1 ), slow and reversible flux decline, and low oil permeate (<20 ppm). In contrast, a commercial superhydrophilic microporous membrane made of mixed cellulose ester suffered severe fouling gradually or immediately when carrying out the emulsion filtrations due to its less than ideal surface properties. It is believed that this class of membranes with desirable superwettability, high flux, and preparation simplicity can be a potential new benchmark for high performance and large-scale oil-water separation in complex environments.