Abstract:The promise of organic ionic plastic crystals (OIPCs) for development of a novel type of gas separation membrane with competitive gas selectivity for CO2/N2 was recently demonstrated. This work aimed to design more selective membranes by investigating a different type of OIPC and a new membrane preparation method. Two different OIPCs were solvent‐cast or co‐cast with poly(vinylidene difluoride) (PVDF), and their gas transport properties were compared. The first OIPC, methyl(diethyl)isobutylphosphonium hexafluorophosphate ([P122i4][PF6]), was previously studied using the co‐cast method, and this was used as a benchmark. The second, N‐methyl‐N‐ethylpyrrolidinium bis(fluorosulfonyl)imide ([C2mpyr][FSI]), was investigated for the first time for gas separation applications, achieving high selectivities (α
>40). The thermophysical properties of the composites indicated that the co‐casting method is a good way to fabricate solid, mechanically stable and durable membranes. Additionally, the enhanced molecular interactions indicated in OIPC/PVDF co‐cast composites point to a new approach for synthesis of other highly selective OIPC‐based membranes.