Cytocompatible polyurethane (PU) surface was prepared by photo-grafting 2-hydroxyethyl acrylate (HEA) onto the membrane surface. Graft polymerization was conducted by combining the use of the photo-oxidation and irradiation grafting. PU membrane was photo-oxidized to introduce the hydroperoxide groups onto the surface, then the membrane, immersed previously in monomer solution, was irradiated under UV light. The ATR-FTIR spectra, element spectroscopy for chemical analysis (ESCA), scanning electron microscopy (SEM) and water contact angle characterized the grafted copolymers and verified the occurrence of graft polymerization. The results showed that UV irradiation could realize the graft polymerization effectively and the grafting was confined within the surface layer. The grafted membrane showed minimal surface morphology. Human umbilical vein endothelial (HUVE) cells were seeded on the grafted surface. The performance of the surface in cell attachment and growth correlated with the oxygen content and mainly the carbonyl content on the surface. Cells were spread more extensively and grew faster on the surface with a higher oxygen content.