While polyethersulfone (PES) represents outstanding oxidative, thermal and hydrolytic stability as well as good mechanical and film-forming properties, the hemocompatibility of PES membranes 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 the PES membrane using the phase separation method, the functional groups of the copolymers migrated and formed a negatively charged coating on the membrane surface. The modified PES membrane blended with a heparin-like block copolymer showed prolonged blood coagulation time and thereby good hemocompatibility. In addition, the clotting time of the modified membrane was enhanced with increasing amounts of the 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 increases due to the addition of heparin-like additives. Thus, the heparin-like surface modification method seemed to be a promising approach for application in the biomedical field.