Recently, much attention has been attracted to bio/blood compatible materials to suppress undesirable biological reactions that determine the fate of living organisms and materials. A phospholipid polymer composed of 2-methacryloyloxyethyl phosphorylcholine (MPC) unit, which is designed by inspiration of cell membrane surface structure, is the most promising polymer biomaterial with excellent bio/blood compatibility. Progress in living radical polymerization method initiated from the surface enables preparation of a dense polymer chains on the surface, which is called as a polymer brush. The polymer brush structure has narrow molecular weight distribution and controlled chain length. So, it is ideal surface to clarify the interactions between the biomolecules and biomaterial surface that has never done. In these regards, the poly(MPC) brush surfaces are expected to be a novel class of biomaterials, and have been extensively studied its unusual properties. In this review, surface-initiated living radical polymerization of MPC and the characteristics of the poly(MPC) brush surfaces are summarized from a viewpoint of biomaterials science.