This work addresses the challenges faced by previous researchers with 6FDA-6FpDA polyimide for propylene/propane separations due to plasticization. A study of film annealing temperature is reported to optimize plasticization suppression in elevated temperature permeation on properly annealed dense films made with high molecular weight polymer. A detailed analysis of pure and mixed gas results using different permeability models is shown in this work. The annealing effects in terms of plasticization suppression and permeability and selectivity changes are discussed in detail. According to our best knowledge, this is for the first time plasticization suppression for propylene/propane has been reported with any polyimide dense film membrane. Results of pure gas sorption experiments using a pressure decay method with un-annealed and annealed films are discussed and used to analyze the permeation data using the dual-mode model. Mixed gas permeation results also are explained with dual mode and bulk flow transport models. © 2010 Elsevier B.V.