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A novel electrolyte membrane PVDF-Al2O3-CsHSO4 usable at medium temperatures was prepared by composite of PVDF and an inorganic proton conductor Al2O3-CsHSO4. The membrane has a steep increase in proton conductivity around 90°C and retains the high conductivity, about 10-3 S•cm-1, up to 200°C. The incorporation of Al2O3-CsHSO4 with PVDF leads to a dramatic improvement of the properties of PVDF, including widen the phase transition temperature of CsHSO4, improve proton conductivity and enhance chemical stability over wide temperature range.