Tetrafluoroethylene (TFE) and perfluoropropylvinyl ether (PPVE) were copolymerized in supercritical carbon dioxide (sc-CO2) with a perfluorodiacyl initiator bis(perfluoro-2-n-propoxypropionyl) peroxide (BPPP). The resultant copolymers with stable perfluoroalkyl end groups were obtained, avoiding the decomposition during processing and applications. Reactivity ratios of TFE and PPVE were first reported. The rTFE and rPPVE values are about 8 and 0.08, respectively. Such parameters are significant for the modification of PTFE through copolymerization of TFE and PPVE. It is found that through increasing the reaction pressure from 8.5 to 25 MPa, while rTFE increases by 12.0%, rPPVE decreases by 9.0%, which should be ascribed to the enhancement of the polarity of CO2 under high pressures. Because the reactivity of TFE is by two orders of magnitude higher than that of PPVE; on one hand, the copolymerization rate falls rapidly with the decrease of TFE feed ratio; on the other hand, TFE content in the copolymer decreases with the reaction time. All copolymers containing different fractions of PPVE enjoy outstanding thermal stability. The DSC result indicates that there exist two forms of crystals with highly regular molecular arrangement or less ordered chain packing which is disturbed by perfluoropropyl pendants. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012