Two ethanoanthracene-based dianhydrides, 9,10-dimethylethanoanthracene-2,3,6,7-tetracarboxylic anhydride (EA-DA) and its more flexible dibenzodioxane-containing derivative (EAD-DA), were synthesized from the same starting material, 9,10-dimethyl-ethanoanthracene-2,3,6,7-tetraol, and used for the preparation of bicyclic intrinsically microporous polyimides (PIM-PIs) by one-pot polycondensation reaction with 3,3′-dimethylnaphthidine (DMN). The resulting organosoluble polyimides, EA-DMN and EAD-DMN, were thermally stable up to 300 °C and had good mechanical properties with tensile strength of 55 and 63 MPa and elongation at break of 15 and 30%, respectively. EA-DMN and EAD-DMN polyimides displayed Brunauer–Emmett–Teller (BET) surface areas of 720 and 800 m2 g–1, respectively. Fresh films showed promising gas separation performance with very high gas permeabilities and moderate gas-pair selectivities, which were both strongly dependent on film thickness. The results obtained in this study shed more light on the relative importance of film thickness and physical aging on faster attainment of the “intrinsic” gas transport properties of high free volume PIM-PIs.