Ethyl cellulose (EC) films that retain lyotropic and thermotropic cholesteric liquid crystalline order, and an amorphous EC film were prepared. The liquid crystalline order was identified by optical measurements. The comparative permeability of oxygen and nitrogen gases for three kinds of EC film was determined, and the applicability of the EC films that retained cholesteric liquid crystalline order to oxygen enrichment are discussed. The permeability of oxygen or nitrogen gas for the liquid crystalline films was lower than that for the amorphous ones. The activation energy for the permeability coefficient of oxygen gas was ca. 3.5 kcal/mol. The ratio of permeability coefficient for oxygen gas to that for nitrogen gas was less than 4. Interestingly, the permselectivity of oxygen and nitrogen gases for the liquid crystalline films was greater than that for the amorphous ones.