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A heparin-like structured macromolecule (HLSM) is synthesized by RAFT polymerization using carboxyl-terminated trithiocarbonate as the RAFT agent. The HLSM can be directly blended with PES in DMAC to prepare flat-sheet membrane by means of a liquid-liquid phase separation technique. The synthesized polymeric material retard blood clotting and the modified membrane exhibits good anticoagulant ability due to the existence of the important functional groups ?SO(3) H, ?COOH and ?OH. The anionic groups on the membrane surface may bind coagulation factors and thus improve anticoagulant ability. The results indicate that the HLSM has potential to improve the anticoagulant properties of biomaterials and to be applied in blood purification including hemodialysis and bioartificial liver supports.