A series of novel perfluorocyclobutyl aryl ether-containing graft copolymers with polystyrene side chains were synthesized by the combination of thermal step-growth [2 pi + 2 pi] cycloaddition polymerization of aryl bistrifluorovinyl ether monomer and atom transfer radical polymerization (ATRP) of styrene. We first synthesized a new aryl bistrifluorovinyl ether monomer of 2-methyl-1,4-bistrifluorovinyloxybenzene in two steps using commercially available 2-methylhydroquinone as starting material and the corresponding perfluorocyclobutyl aryl ether-based homopolymer with methoxyl end groups was prepared through the homopolymerization of this monomer in diphenyl ether. Next, the pendant methyls of this fluoropolymer were mono-brominated by N-bromosuccinimide and benzoyl peroxide so as to be converted to ATRP initiation groups. The targeted poly(2-methy1-1,4-bistrifluorovinyloxybenzene)-g-poly-styrene with relatively narrow molecular weight distributions (M-w/M-n <= 1.38) was obtained by the combination of bulk ATRP of styrene at 110 degrees C using CuBr/bpy as catalytic system and the grafting-from strategy. These fluorine-containing graft copolymers show excellent solubility in common organic solvents. (C) 2010 Elsevier Ltd. All rights reserved.