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We report a scalable synthesis of high-molecularweight poly(arylene ether)s (PAEs) using decafluorobiphenyl under SNAr reaction conditions and the preparation of enantiopure (R,R)-6,11-di(tert-butyl)triptycene-1,4-hydroquinone. The nonfluorinated biphenyl-based PAE was also synthesized using Pdcatalyzed C−O coupling methods, and structure−property comparisons were made from the different biphenyl-based polymers. The integration of free-volume-promoting triptycene moieties on the main chain gives rise to intrinsic porosity, which can be further modulated by incorporating biphenyl or perfluorobiphenyl comonomers. The nonfluorinated PAE exhibited a BET surface area of 270 m2 g−1, whereas the racemic and enantiopure fluorinated PAEs showed higher BET surface areas of 454 and 368 m2 g−1, respectively. WAXS analysis revealed that all of the polymers tested have a greater disruption of chain packing compared to related polyimides, with the fluorinated PAEs having the highest average interchain spacing. The fluorinated PAEs also demonstrated high gas permeability as a result of their free volume. The triptycene-based PAEs also were resistant to plasticization even at CO2 pressures of ∼31 bar.