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Hydrophilic polymers with low affinity for foulants were broadly utilized as functional membrane surface modifiers to mitigate fouling owing to superior hydration capability. Herein, novel hydrophilic hyperbranched poly(N-acryoyl morpholine) (HPA) synthesized through one-step RAFT polymerization was immobilized onto commercial PVDF microfiltration membrane surface using biomimetic adhesion polydopamine as an intermediate reaction platform. The surface composition and morphology of HPA decorated membranes (M-PD/HPA) were examined, demonstrating that the nano-sized HPA was facilely anchored on the membrane surface without obviously changing membrane pore size and distribution. In comparision with hydrophobic pure membrane (M-PVDF), hydrophilic and underwater superoleophobic M-PD/HPA exhibited excellent multiple defense capability toward oil, protein and bacteria due to the presence of a steric repulsive barrier of hydrated HPA layer. For model hexane-in-water emulsion separation at 0.02 MPa, permeation flux of M-PD/HPA up to 149.8 L m−2 h−1 was improved by three times and the rejection was up to 99.5%. Importantly, for the separation of complex artificial oily wastewater, relevant flux reduction of M-PD/HPA was decreased from 60.9% of M-PVDF to 36.8% and flux recovery ratio of M-PD/HPA was increased from 34.8% to 82.6%. Therefore, M-PD/HPA has a promising prospect for emulsified oil separation and water purification. Unlabelled Image • Novel hydrophilic hyperbranched Poly(N-acryoyl morpholine) (HPA) synthesized by one-pot RAFT. • HPA was immobilized on membrane surface via biomimetic adhesive chemistry. • HPA coating simultaneously enhanced surface hydrophilicity and roughness. • HPA modified membrane with enhanced separation and antifouling performance. [ABSTRACT FROM AUTHOR]