Two novel iptycene-based tetramine monomers were successfully synthesized by nucleophilic aromatic substitution of triptycene-1,4-diol and pentiptycene-6,13-diol with 5-chloro-2-nitro-aniline, followed by reduction, respectively. These monomers were polymerized with 4,4-binaphthyl-1,1,8,8-tetracarboxylic dianhydride to obtain two novel iptycene-based poly[bis(benzimidazobenzisoquinolinones)]s (PBIBI -TPD and PBIBI-PPD) by a one-step, high-temperature solution polycondesation. Incorporation of iptycene groups especially the pentiptycene group in the polymer backbones improved their solubility and thermal stability. The resulting membranes exhibited good gas permeability owing to the high internal free volume elements introduced by the iptycene groups as well as high gas selectivity due to the restricted local segmental mobility arising from the interlocking of these groups in the polymer backbone. The membrane of PBIBI PPD showed high CO2 permeability (112 barrer) and moderately good CO2/N-2 and CO2/CH4 selectivity (22 and 31) for mixed gas separation. (C) 2013 Elsevier Ltd. All rights reserved.