Tetrafiuoroethylene (TFE) and hexafluoropropylene (HFP) were subjected to reactions with freshly distilled sulfur trioxide to obtain 1-fluorosulfonyldifluoro-acetylfluoride (FSDFAF, yield 65–70%) and pentafluoro-2-propenylfluorosulfate (PPFS, yield up to 50%). A subsequent reaction of FSDFAF with PPFS under anhydrous conditions led to a preparation of 2-(1-pentafluoro-2-propenyloxy)tetrafluoroethanesulfonyl fluoride (PPOTESF, yield 40–41%) whose structure was proved by both infrared (IR) spectroscopy and nuclear magnetic resonance (19F NMR). TFE was copolymerized with PPOTESF in bulk by using a free radical initiator of the hydrocarbon type at a temperature of 50°C. Various TFE/PPOTESF mole ratios were employed and the presence of sulfonyl fluoride ([BOND]SO2F) functional groups in the copolymers was proven by IR spectroscopy. The copolymers were subjected to alkaline hydrolysis and the [BOND]SO2F content was found not to exceed 0.70–0.80 mEq/g with polymer yields in the range of 11–31%. The reactivity ratios r1 and r2 related to TFE and PPOTESF, respectively, were determined by using the Fineman-Ross method. A random distribution of PPOTESF units along the polymeric chain, consisting mainly of TFE fragments, was found to exist. The copolymers had melting temperatures 40–45°C lower than polytetrafluoroethylene and were thermally stable to 305–315°C. © 1993 John Wiley & Sons, Inc.