A novel inorganic proton exchange membrane based on phosphoric acid (PA)-functionalized sintered mesoporous silica, PA-meso-silica, has been developed and investigated. After sintering at 650 °C, the meso-silica powder forms a dense membrane with a robust and ordered mesoporous structure, which is critical for retention of PA and water within the porous material. The PA-meso-silica membrane achieved a high proton conductivity of 5 × 10(-3) to 5 × 10(-2) S cm(-1) in a temperature range of 80-220 °C, which is between 1 and 2 orders of magnitudes higher than a typical membrane Nafion 117 or polybenzimidazole (PBI)/PA in the absence of external humidification. Furthermore, the PA-meso-silica membranes exhibited good chemical stability along with high performance at elevated temperatures, producing a peak power density of 632 mW cm(-2) using a H2 fuel at 190 °C in the absence of external humidification. The high membrane proton conductivity and excellent fuel cell performance demonstrate the utility of PA-meso-silica as a new class of inorganic proton exchange membranes for use in the high-temperature proton exchange membrane fuel cells (PEMFCs).