Proton exchange membranes with chemically tolerant organically modified zirconia are prepared by inorganic-organic self-assemble sol-gel process. The monomers were covalently bonded at the zirconia interface to form macromolecular inorganic-organic networks. The modified inorganic-organic hybrid membranes showed high flexibility, chemical tolerance, mechanical property and thermal stability up to 325 degrees C. For the proton exchange membrane, the organically modified hybrids were put into the condition of room temperature or boiled in 85% H3PO4 at 150 degrees C. The proton conductivity of the ion exchange membranes was investigated. (c) 2006 Elsevier B.V. All rights reserved.