Inspired by mussel adhesion chemistry, a kind of hydrophilic poly(vinylidene fluoride) (PVDF) microfiltration membrane with underwater superoleophobicity was prepared using thiolated hyperbranched zwitterionic poly(sulfobetaine methacrylate) (HPS) as a nanoscale surface modifier. The HPS was first synthesized via reversible addition fragmentation chain transfer (RAFT) copolymerization and followed by sulfonation reaction and then coated onto polydopamine (PD) adhesive PVDF membranes via thiol-mediated Michael addition reaction. The successful and uniform coating of HPS onto the membrane surface was demonstrated by X-ray photoelectron spectroscopy and by using an energy dispersive X-ray detector. The surface micro nano morphology and increased roughness of the PD/HPS-modified (M-PD/HPS) membrane were also investigated by using a field emission scanning electron microscope and an atomic force microscope. The M-PD/HPS membrane could be wetted completely by water, and the underwater oil contact angles were about 160, indicating the M-PD/HPS membrane has excellent hydrophilicity and underwater superoleophobicity. Compared with the pure PVDF membrane, the M-PD/HPS membrane for hexane-in-water emulsion separation exhibited an enhanced water filtration flux of 10 707 L m(-2) h(-1) (0.1 MPa), and the oil rejection ratio was above 99.9%. Besides, the excellent antifouling ability and recyclable properties of the M-PD/HPS membranes would make them suitable for long-time use. Thus, the approach of mussel adhesion chemistry employing the RAFT-mediated nanosized hyperbranched zwitterionic polymers as postmodification reagents showed a good application prospect in purification of oily waste water and oil recovery.