Nafion-SiO2 hybrid electrolytes were synthesized by sol gel reaction. The homogeneity, structural properties, and proton conductivity of the hybrid membranes were studied. Small-angle scattering analyses indicate that the Nafion structural matrix was preserved on the nanoscale, and the growth of silica particles occurred both in the ionic and nonionic domains of Nafion, which resulted in hybrids with characteristic morphologies. The water uptake and the weight fraction of the inorganic phase were found to be dependent on the alcohol solvent used for the sol gel synthesis. Nafion-silica hybrids with homogeneous distribution of the inorganic phase were obtained using methanol as the solvent for the sol-gel reaction. The observed microstructural properties of the Nafion-silica membranes were related to enhanced proton conductivity at high temperatures and low relative humidity conditions. (C) 2014 Elsevier B.V. All rights reserved.