A novel approach for the surface modification of poly(acrylonitrile-co-2-hydroxyethyl methacrylate) (PANCHEMA) membranes by introducing phospholipid moieties is presented, which involved the reaction of the hydroxyl groups on the membrane surface with 2-chloro-2-oxo-1,3,2-dioxaphospholane (COP) followed by the ring-opening reaction of COP with trimethylamine. The chemical changes of phospholipid-modified acrylonitrile-based copolymers (PMANCP) membranes were characterized by Fourier transfer infrared spectroscopy and X-ray photoelectron spectroscopy. The surface properties of PMANCP membranes were evaluated by pure water contact angle, protein adsorption, and platelet adhesion measurements. Pure water contact angles measured by the sessile drop method on PMANCP membranes were obviously lower than those measured on the PANCHEMA membranes and decreased with the increase of the content of phospholipid moieties on the membrane surface. It was found that the bovine serum albumin adsorption and platelet adhesion were suppressed significantly with the introduction of phospholipid moieties on the membranes surface. These results demonstrated that the described process was an efficient way to improve the surface biocompatibility for the acrylonitrile-based copolymer membrane.