Inorganic−organic hybrid membranes with anhydrous proton conduction were prepared from 3-aminopropyltriethoxysilane and H2SO4 by the sol−gel method. The membrane has a unique structure: a hexagonal phase formed by the stacking of rodlike polysiloxanes with ion complexes of ammonium groups and HSO4- extruded outside. The membranes showed high conductivity of 2 × 10-3 S cm-1 at 200 °C under dry atmosphere. In the membrane, protons probably migrate through the outside of the rodlike polysiloxanes along hydrogen-bond chains formed among HSO4- anions.