A novel amphiphilic fluorinated gradient copolymer was prepared by semibatch reversible addition fragmentation chain transfer (RAFT) method using poly (ethylene glycol) methyl ether methacrylate (PEGMA) and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate (TFOA) as monomers. The resultant amphiphilic copolymers were then incorporated into the poly(ether sulfone) (PES) to fabricate PES blend membranes via the non-solvent-induced phase separation method (NIPS). During the phase inversion process, both hydrophilic (PEGMA) and low surface energy (TFOA) segments significantly enriched on the membrane surface by surface segregation to form an amphiphilic surface, which was demonstrated by surface wetting properties and X-ray photoelectron spectroscopy (XPS) measurements. According to the filtration experiments of oil-in-water emulsion, the heterogeneous membranes exhibited superior oil-fouling resistant properties, that is, low flux decay (as low as 15.4%) and high flux recovery (almost 100%), compared to the pure PES membrane. The synergistic effect of fouling-resistant and fouling-release mechanisms was found to be responsible for the excellent antifouling capacities. The findings of this study offer a facile and robust strategy for fabricating ultralow oil-fouling membranes that might be used for effective oil/water separation.