In this study, a reaction enhanced surface segregation method was explored for in-situ construction of antifouling separation layer on membrane surface. Polyvinyl pyrrolidine (PVP) is used as the surface segregation agent in the casting solution and polyacrylic acid (PAA) is used as the additive in the coagulation bath. During the membrane formation process, PVP and PAA spontaneously migrate to the surface of the polyvinylidene fluoride (PVDF) support in an opposite direction and form a crosslinked separation layer based on the hydrogen bonding interaction. The resultant layer has smaller effective pore size and higher hydrophilicity compared with the PVDF control membrane, which renders enhanced antifouling and separation performance. In the ultrafiltration of oil-water emulsion, the rejection was 100%, the initial water flux was 695 +/- 33 L m(-2) h(-1) bar(-1), and the FRR was 95.2%; meanwhile, in the ultrafiltration of BSA solution, the rejection was 90.3%, the initial water flux was 603 +/- 18 L m(-2) h(-1) bar(-1) and the FRR was 92.3%. This study offered a novel and facile method for antifouling membrane surface construction. (C) 2018 Elsevier Ltd. All rights reserved.