Cationic UV-curable methacrylate copolymers consisting of glycidyl methacrylate, iso-butyl methacrylate, and 2,2,3,4,4,4-hexafluorobutyl methacrylate were synthesized, and their structures were characterized by FTIR, (1)H NMR, and (13)C NMR. A series of UV-cured composite films based on the synthesized copolymers and an alicyclic epoxy resin, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (CE) were obtained through photopolymerization. Their surface contact angle, chemical ability, gloss, light transmittance, thermal behavior, micromorphology, and shrinkage were investigated. Results indicated that these cured resins showed excellent gloss and visible light transmittance; after the combination of the copolymers and CE, and in the presence of fluorine in the curing systems they exhibited relatively fine water resistance, chemical, and thermal stability. It was observed that these copolymers could decrease the degree of the volume shrinkage to CE. The UV-curable materials may have promising applications in optical fiber coatings, flip chip and Organic Light-Emitting Diode (OLED) packing. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 123: 1724-1731, 2012