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Abstract: The development of anhydrous proton conducting membrane is important for the operation of polymer electrolyte membrane fuel cell (PEMFC) at intermediate temperature (100–200°C). In this study, we have investigated the acid–base hybrid materials by mixing of strong phosphonic acid polymer of poly(vinylphosphonic acid) (PVPA) with the high proton-exchange capacity and organic base of heterocycle, such as imidazole (Im), pyrazole (Py), or 1-methylimidazole (MeIm). As a result, PVPA-heterocycle composite material showed the high proton conductivity of approximately 10−3 Scm−1 at 150°C under anhydrous condition. In particular, PVPA-89mol% Im composite material showed the highest proton conductivity of 7×10−3 Scm−1 at 150°C under anhydrous condition. Additionally, the fuel cell test of PVPA-89mol% Im composite material using a dry H2/O2 showed the power density of approximately 10mWcm−2 at 80°C under anhydrous conditions. These acid–base anhydrous proton conducting materials without the existence of water molecules might be possibly used for a polymer electrolyte membrane at intermediate temperature operations under anhydrous or extremely low humidity conditions. [Copyright &y& Elsevier]