Perfluorourethane copolymers were synthesized by free-radical copolymerization using a fluorine-containing monomer and urethane monomers as starting materials. The fluorine-containing monomer used was perfluoroalkyl alcohol(FOH), and the urethane monomers used were tolylene 2,4-diisocyanate(TDI), hexamethylene diisocyanate(HDI), and 4,4-methylene bis(phenyl isocyanate)(MDI). The surface properties and surface modification ability of the perfluorourethane copolymers prepared were investigated. The surface free energies of polyethylene(PE) films modified by the perfluorourethane copolymers and their surface modification properties were also investigated.