New alternating copolymers comprising a chlorotrifluorinated backbone and imidazole-terminated pendant ethylene oxide groups have been prepared with a view to their use as a component of proton-conducting membranes in polymer electrolyte fuel cells. A vinyl ether containing an imidazole (Imi) function protected by a benzyl group (BVI) was first synthesized in a three-step reaction. It was then copolymerized in solution with chlorotrifluoroethylene (CTFE) by conventional radical copolymerization leading to alternating poly(BVI-alt-CTFE) copolymers in good yields. Deprotection of the benzyl group under hydrogen produced a chlorotrifluorinated poly (Imi-alt-CTFE) copolymer. The polymer was subsequently used to form blend membranes with sulfonated poly(ether ether ketone) (sPEEK). The conductivity of blend membranes of poly (Imi-alt-CTFE) with sPEEK lies in the range of 4-10 mS cm(-1) at 40-70 degrees C and, for blend membranes rich in poly(Imi-alt-CTFE), is little dependent on relative humidity between 30 and 100%. It is surmised that the polymer and membrane composition favor microstructural phase separation into chlorotrifluorinated polymer backbone domains and regions in which imidazole groups are clustered. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 223-231, 2010