Poly(epichlorohydrin-g-styrene) and poly (epichlorohydrin-g-methyl methacrylate) graft copolymers were synthesized by a combination of cationic and photoinitiated free-radical polymerization. For this purpose, first, epichlorohydrin was polymerized with tetrafluoroboric acid (HBF4) via a cationic ring-opening mechanism, and, then, polyepichlorohydrin (PECH) was reacted ethyl-hydroxymethyl dithio sodium carbamate to obtain a macrophotoinitiator. PECH, possessing photolabile thiuram di-sulfide groups, was used in the photoinduced polymerization of styrene or methyl methacrylate to yield the graft copolymers. The graft copolymers were characterized by H-1-NMR spectroscopy, differential scanning calorimetry, and gel permeation chromatography. (c) 2007 Wiley Periodicals, Inc.