A series of polyimides including a non-coplanar moiety were synthesized in order to investigate the effect on gas permeability and selectivity. The gas permeation properties of He, H-2, O-2, N-2, CH4 and CO2 were measured using a constant-volume method. Only 6FDA-terphenyl consisting of laterally attached phenyl groups shows a substantial increase because its terphenyl moiety is a rigid structure with a high aspect ratio. The order of permeability increase from 6FDA-phenyl to 6FDA-terphenyl is consistent with the calculated fraction free volume and measured permittivity. It is observed that the most gain in permeability for 6FDA-terphenyl polyimide arises from the enhancement in apparent diffusion coefficient, while the permeability increase for 6FDA-biphenyl is mainly due to the increase in solubility. A relationship of diffusivity vs. gas penetrant size as well as gas solubility vs. critical temperature of gas penetrant was also investigated. (C) 2003 Elsevier Science Ltd. All rights reserved.