While polyethersulfone (PES) represents outstanding oxidative, thermal and hydrolytic stability as well as good mechanical and film-forming properties, the hemocompatibility of PES membrane must be dramatically enhanced to reduce injections of anticoagulants during hemodialysis. In this study, a series of biological macromolecules with heparin-like chains were synthesized via reversible addition fragmentation chain transfer (RAFT) polymerization to design anticoagulant membrane surfaces. When the synthesized copolymers were used as additives to modify PES membrane using phase separation method, the functional groups of the copolymers migrated and formed a negative charged coating on the membrane surface. The modified PES membrane blended with heparin-like block copolymer showed prolonged blood coagulation time and thereby good hemocompatibility. In addition, the clotting time of the modified membrane was enhanced prolonged with the increasing of heparin-like amphiphilic tri-block copolymer. Furthermore, the results of the cell morphology and the 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay suggest that the cytocompatibility increase due to the addition of heparin-like additives. Thus, the heparin-like surface modification method seemed to be a promising approach to be applied in biomedical field.