A series of novel perfluorocyclobutyl aryl ether-containing graft copolymers with polystyrene side chains were synthesized by the combination of thermal step-growth [2π + 2π] 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
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