A novel catalyst system of Reverse Atom Transfer Radical Polymerization (RATRP) to prepare Polyurethane (PU) films modified by poly(2-methacryloyloxyethyl phosphorylcholine) (pMPC) was studied in this article. In this system, PU film was pretreated by LaCl3/CA ethanol solution to obtain a hydrated surface allowing more initiators to be immobilized on it. Moreover, complexes composed of silane coupling agent 3-chloropropyltrimethoxysilane (CPTM), chlorhexidine acetate (CA) and lanthanum(III) worked as ligands of copper ions as a whole during RATRP process. PU films before and after modification were characterized by X-ray photoelectron spectroscopy (XPS) and static contact angle (SCA) to confirm that pMPC chains were successfully grafted from the substrates. Results of Plasma recalcification time assay, platelet adhesion test indicated excellent blood compatibility. Furthermore, the antibacterial activity of the material have been improved which proved by adhesion test of E.coil.