Maleimide groups are synthesized on the surface of PE films by means of two different routes, from oxidized and anhydride-grafted PE films. Maleimide groups covalently bonded to the surface of PE film were used as photopolymerization initiators of acrylic acid (AA) and glycidyl methacrylate (GMA). The formation of poly (acrylic acid) (PAA) and poly (glycidyl methacrylate) (PGMA) covalently bonded to the modified PE film surface by the photopolymerization process was demonstrated by ATR-FTIR, gravimetry, and SEM results. The thickness of the polymer layers formed in the polymerization depends on the irradiation time. The PAA layer formed in the polymerization is thinner than 250 nm, whereas that of PGMA in some case is thicker than 3 mum.