The phosphosilicate gels derived from the mixture of 2-(diethoxyphosphoryl)ethyltriethoxysilane (DPTS) and tetraethoxysilane (TEOS) showed a high proton conductivity after a heat treatment at 450 degreesC. The high conductivity was brought by the generation of large amounts of isolated orthophosphoric acid in the gels due to the thermal decomposition of DPTS.