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Flexible and temperature tolerant organic-inorganic nano-hybrid membranes using metal oxides and organic monomers have been synthesized by sol-gel processes. The membranes showed enhanced thermal stability up to 300degC due to the presence of cross-linkable inorganic nano-phase in the hybrid macromolecular matrix. The membrane becomes proton conducting polymer electrolytes when doped with 12-phosphotungstic or phosphoric acids. The proton conducting properties of the hybrid membranes were measured in the temperature range from room temperature to 160degC under saturated humidity conditions. The modified organic-inorganic hybrid membranes could be applied to temperature tolerant proton conducting PEFCs.