Heparin (HEP) and phosphorylcholine groups (PC) were grafted onto the polyurethane (PU) surface in order to improve biocompatibility and anticoagulant activity. After the surface grafting sites of PU were amplified with the primary amine groups of polyethylenimine (PEI), heparin was covalently linked onto the surface by the reaction between the amino group and the carboxyl group. PC groups were covalently immobilized on the PU-PEI surface through the reaction between the amino group and the aldehyde group of phosphorylcholine glyceraldehyde (PCGA). The surface density of primary amine groups was determined by a ninhydrin assay. The amino group density reached a maximum of 0.88 μmol/cm2 upon incorporation of 10 wt% PEI. The amount of heparin covalently immobilized on the PU-PEI surface was determined by the toluidine blue method. The grafting chemistry resulted in the comparatively dense immobilization of HEP (2.6 μg/cm2) and PC to the PU-PEI surfaces. The HEP and PC modified surfaces were characterized by water uptake (PU 0.15 mg/cm2, PU-PEI 3.54 mg/cm2, PU-HEP 2.04 mg/cm2, PU-PC 2.38 mg/cm2), water contact angle (PU 95.3°, PU-PEI 34.0°, PU-HEP 39.5°, PU-PC 37.2°), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and scanning electron microscope (SEM). The results demonstrated that the PUPEI surface was successfully grafted with HEP and PC. The hydrophilicity and hemocompatibility of these grafted surfaces were significantly improved. These results suggested that the PU-HEP and PU-PC composite films are promising candidates for blood contacting tissue engineering.