The composite material of heteropolyacid (12-phosphotungstic acid; PWA) and polystyrene sulfonic acid (PSS) construct the PWA-encapsulated material by the self-assembly of -SO3H onto the PWA surface; as a result, the fast proton transfer occurred at the interface between the PWA and -SO3H, and the encapsulated material indicated the high anhydrous proton conductivity of 1 x 10(-2) S cm(-1) at 180 degrees C. These anhydrous proton-conducting materials without the existence of water molecules are quite different from customary ion-exchange membrane, such as Nafion, and may have advantages as an electrolyte membrane for polymer electrolyte membrane fuel cells operating at intermediate temperatures under anhydrous conditions but also for electrochemical devices including electrochromic displays, chemical sensors, and others.