We examined the relation of gas permeabilities, diffusivities, and solubilities with the structures in various polyimide films. Permeability coefficients (P) and diffusion coefficients (D) of polyimides were measured by the use of the high vacuum time-lag method. Glass transitions, d-spacings, and densities of polyimides were determined from the data with a differential scanning calorimetry, a wide angle X-ray diffraction, and a density gradient column method, respectively. The films tested were made from 32 kinds of polyimides, which were synthesized from the reactions of various diamines containing biphenyl, diphenylmethane, phenylether, diphenyl sulfone, or diphenyl sulfide structures with BPDA, 6FDA, or PMDA. The effect of ordered region in polyimide films on gas diffusivities were also examined. A number of polyimide films gave the decreased diffusivities and solubilities due to the occurrence of ordered region when they were annealed over glass transition temperatures. We discussed especially diffusivities and structures of amorphous states of other polyimides except for these polyimides having ordered region. Furthermore, the relation of D having large effect on permeability, with physical parameters, such as d-spacings and fractional free volumes (V-f), was examined in amorphous state. However, we could not find good correlations between In D and d-spacing or V-f(-1). Especially, these poor correlations were observed in polyimides containing polar substituents. The results show that the gas diffusion of glassy polymers may not be interpreted only in terms of total free space or mean segment distance.