We examined the influence of polyaniline (PAn)’s unit sequence and doping with low molecular weight dopants or polymer dopants on permeation property. It was found that CO2 permeability was increased by the formation of a quinonediimine unit in PAn with the oxidation. CO2 sorption amount of PAn was decreased by oxidation. The increase of CO2 permeability with oxidation, therefore, resulted from the increase of diffusivity, which was attributable to morphological variation by the increase of a quinonediimine unit. The permselectivity of PAn films was found to be remarkably improved by doping. In particular, the selectivity value of the PAn film doped with polyvinyl sulphonic acid as a polymer dopant went up to over 2,000. This remarkable increase of selectivity was found to result in the increase of selectivity, depending on diffusivity. It was also found that the permselectivity of the PAn film doped by polymer dopants was surpassed, as compared with that doped by low molecular dopants.