Highly proton conductive polymers have long attracted the attention of researchers for use in energy conversion, sensors, catalysts, and other applications. From the viewpoint of the scientific history of the creation of highly proton conductive polymers, one fundamental approach is based on the strategy of phase-segregated structures with strong acid groups. This Feature Article presents a new approach to enhancing the proton conductivity of the polymer thin films using an interface that can modify the degrees of freedom for a polymer structure through interaction between the substrate surface and polymers. I introduce suppressed proton conductivity into Nafion thin films and then specifically examine the enhancement in proton conductivity by the molecular orientation of the polymers. As the last topic, a highly proton conductive organized polyimide thin film is demonstrated using the lyotropic liquid-crystal property. Both molecular ordering and the in-plane oriented structure can enhance proton conductivity. Moreover, the optical domain and degree of molecular ordering derived from the molecular weight can contribute strongly to the proton transport property.