A series of novel graft copolymers consisting of perfluorocyclobutyl aryl ether-based backbone and poly(methyl methacrylate) side chains were synthesized by the combination of thermal [2 pi + 2 pi] step-growth cycloaddition polymerization of aryl bistrifluorovinyl ether monomer and atom transfer radical polymerization (ATRP) of methyl methacrylate. A new aryl bistrifluorovinyl ether monomer, 2-methyl-1,4-bistrifluorovinyloxy-benzene, was first synthesized in two steps from commercially available reagents, and this monomer was homopolymerized in diphenyl ether to provide the corresponding perfluorocyclobutyl aryl ether-based homopolymer with methoxyl end groups. The fluoropolymer was then converted to ATRP macroinitiator by the monobromination of the pendant methyls with N-bromosuccinimide and benzoyl peroxide. The grafting-from strategy was finally used to obtain the novel poly(2-methyl-1,4-bistrifluorovinyloxybenzene)-g-poly(methyl methacrylate) graft copolymers with relatively narrow molecular weight distributions (M-w/M-n <= 1.46) via ATRP of methyl methacrylate at 50 degrees C in anisole initiated by the Br-containing macroinitiator using CuBr/dHbpy as catalytic system. These fluorine-containing graft copolymers can dissolve in most organic solvents. This is the first example of the graft copolymer possessing perfluorocyclobutyl aryl ether-based backbone. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 11-22, 2011