Sulfonation of poly(ether sulfone) was carried out with chlorosulphonic acid in chloroform and its composite proton-exchange membrane was prepared using aminopropyltriethoxysilane as inorganic precursor by sol-gel in acidic medium. These membranes were further subjected to phosphorylation with phosphorous acid for introducing phosphonic acid functionality at inorganic segment. Extent of sulphonation was estimated by H-1-NMR spectroscopy while introduction of phosphonic acid groups was confirmed by FTIR spectroscopy and ion-exchange capacity studies. Different membranes, with varied silica content without and with phosphorylation, were characterized for their thermal and mechanical stabilities, physicochemical and electrochemical properties using thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), scanning electron microscopy (SEM), aq. methanol uptake studies, proton conductivity and methanol permeability measurements. The silica content in the membrane matrix and effect of phosphorylation was optimized as a function of membrane properties. Activation energy required for the proton transport across the membrane was also estimated and found to be comparable with Nafion 117 membrane. From the frictional interpretation and estimation of selectivity parameter it was observed that SPS-Si composite phosphorylated membrane with 20% silica content (SPS-Si(P)/20) resulted in the best proton-exchange membrane, which exhibited quite higher selectivity parameter in comparison to Nafion 117 for direct methanol fuel cell applications. Also, current-voltage polarization characteristics of SPS-Si(P)/20 membrane measured in direct methanol fuel cell, were found to be comparable to the Nafion 117 membrane. (c) 2006 Elsevier B.V. All rights reserved.