A strong effect of the chemical composition and imidization method, on physical and especially on gas transport properties of polyimides was demonstrated. Two fluorinated diamines 6FpDA and bisAPAF were polymerized in different ratios, employing the fluorinated dianhydride 6FDA to, get polyimides with nine different compositions. For all synthesized materials three imidization methods were used: azeotropic, thermal, and-chemical. The 6FDA-6FpDA homopolymers showed significant differences in the gas transport properties, indicating the influence of the imidization route on the final properties of the polyimides. For polyimides containing bisAPAP, the chemical composition played an important role due to the exchange of the hydroxyl groups by acetate groups leading to different interchain interactions. The gas transport was mainly controlled by the chain packing for thermally and azeotropically imidized polymers with bisAPAF contents lower than 30 mol %. For bisAPAF contents above 50 mol % the gas transport was controlled by the intermolecular interactions, e.g., hydrogen bonds.