We reported the fabrication of a highly hydrophilic nanometer-scale modified surface on the inert polymer substrate by photo-induced graft polymerization of 2-methacryloyloxyethyl phosphorylcholine (MPC) to obtain biocompatible surfaces. As substrates, poly(ether-ether-ketone) (PEEK) were used. Photoinduced radical formation on the substrate could be realized without any photosensitizer because of the benzophenone units in PEEK molecular structure, which acts as a photo-initiator during the graft polymerization. The poly(MPC)(PMPC)-grafted PEEK surface fabricated by a novel and simple polymerization system exhibited unique characteristics such as high wettability and high anti-protein adsorption, which makes it highly suitable for medical applications.