A novel proton conductor has been realized by employing a ternary polymer blend system in combination with an electric-field orientation technique. A polymer film recast from a solution containing poly(acrylic acid), poly(vinyl butyral), and fluoroalkyl craft polymer under 2 kV(.)cm(-1) exhibited 10 times higher proton conductivity than that prepared without the external electric field. However, when the film was prepared under a field higher than 4 kV(.)cm(-1), proton conductivity decreased. The membranous character has been investigated by SEM and AFM observations. As a result, it has been proven that an electric-field treatment of 2 kV(.)cm(-1) forms the largest hydrophilic domains for proton conduction in the film. The alteration of the phase separation morphology induced by the electric field well explains the proton conductivity change.