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Four spirobichroman-based polyimides (6FDA-F, 6FDA-O, 6FDA-P, and 6FDA-M) were successfully obtained via polyreaction between diamines of different substituents (-H, -OCH3, -N, and -CH3) and 4,4′-(hexafluoroisopropylidene)-diphthalic anhydride (6FDA). The molecular weights, thermophysical, dihedral angle of the molecules, fractional free volume, d-spacing, Brunauer–Emmett–Teller surface area, and gas separation performance were studied through a combination of experiments and molecular dynamics simulations. These polymers show high molecular weights, with number-average molecular weights (Mn) in the range of 5.0–15.3 × 104, and excellent thermal stability, with weight loss temperatures (T5%) of over 420 °C. The pure-gas (O2, N2, CO2, and CH4) permeation results indicated that the four polymers selectivity of CO2/CH4 over 31 and that 6FDA-F had the highest gas permeability among the four tested gases. Importantly, the dihedral angle from molecular simulation was used to clarify the phenomenon wherein the 6FDA-P gas permeability lower than 6FDA-F. A detailed analysis indicates that -CH3 increased the gas permeability of the polyimides, while the turnstile-like rotary thermal motion of -OCH3 formed channel obstacles and improved the gas selectivity. The polymers containing pyridine ring and those containing benzene ring follows different gas separation mechanisms, based on the gas solution-diffusion behaviour.