Proton-conducting hybrid materials composed of silica and Nafion polymer were prepared from the sol-gel synthesis of silica in aqueous Nafion solution. The compositions of hybrid proton conductors were adjusted with the changing ratios of tetraethyl orthosilicate to Nafion. The thermal analysis, FTIR, SEM, and X-ray diffraction studies have proved the formation of Nafion/silica hybrid materials and no remarkable phase separation was observed, which led to an assumption that the macromolecular chain of silica and Nafion was homogeneously interlaned.