Separation of high-pressure carbon dioxide from fluorocarbons is important for the production of fluoropolymers such as poly(tetrafluoroethylene). Typical polymeric membranes plasticize under high CO2 partial pressure conditions and fail to provide adequate selective separations. Torlon, a polyamide-imide polymer, with the ability to form interchain hydrogen bonding, is shown to provide stability against aggressive CO2 plasticization. Torlon membranes in the form of asymmetric hollow fibers (the most productive form of membranes) are considered for an intended separation of CO 2/C2F4. To avoid safety issues with tetrafluoroethylene (C2F4), which could detonate under testing conditions, safer surrogate mixtures (C2H2F 2 and C2H4) are considered in this paper. Permeation measurements (at 35 °C) indicate that the Torlon membranes are not plasticized even up to 1250 psi of CO2. The membranes provide mixed gas CO2/C2H2F2 and CO 2/C2H4 selectivities of 100 and 30, respectively, at 1250 psi partial pressures of CO2. On the basis of the measured separation performances of CO2/C2H 2F2 and CO2/C2H4 mixtures, the selectivity of the CO2/C2F4 mixture is expected to be greater than 100. Long-term stability studies indicate that the membranes provide stable separations over a period of 5 days at 1250 psi partial pressures of CO2, thereby making the membrane approach attractive. © 2009 American Chemical Society.