Bis(hexafluoroisopropyl) fumarate (BHFIPF) did not homopolymerize with free radical initiators. However, BHFIPF yielded alternating copolymers with styrene in bulk with Azobisisobutyronitrile (AIBN) as a radical initiator. The monomer reactivity ratios of BHFIPF (M(1)) and styrene (M(2)) were calculated as r(1) = 0.00 and r(2) = 0.02. BHFIPF also copolymerized with vinyl pentafluorobenzoate (VPFB) in bulk and in pentafluoroisopropanol solution to produce an alternating copolymer. The reactivity ratios of BHFIPF (M(1)) with VPFB (M(2)) were r(1) = 0.00 and r(2) = 0.05 in bulk and r(1) = 0.01 and r(2) = 0.11 in pentafluoroisopropanol, respectively. The glass transition temperatures (T(g)) of the BHFIPF-styrene and BHFIPF-VPFB copolymers were 107 and 86 degrees C, respectively. The BHFIPF-styrene copolymer was thermally stable, and the thermal degradation temperature (T(d)) was 400 degrees C, whereas the T(d) of BHFIPF-VPFB copolymer was 240 degrees C. The films obtained by casting from tetrahydrofuran (THF) solutions of these copolymers were flexible and transparent. Their refractive indices were 1.4048 for the BHFIPF-styrene copolymer, and 1.3980 for the BHFIPF-VPFB copolymer at 633 nm, respectively. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 2834-2838, 2011