A series of proton conductive composite membranes based on poly(vinyl alcohol) and phosphosilicate gels powders were successfully prepared. The proton conductivity of these composite was attributed to the phosphosilicate gel, which derived from tetraethoxysilane and phosphoric acid by sol-gel process at a molar ratio of P/Si = 1.5. The proton conductivity increased with increasing both the content of phosphosilicate gel and relative humidity. Temperature dependence of conductivity showed a Vogel-Tamman-Fulcher type behavior, indicating that proton was transferred through a liquidlike phase formed in micropores of phosphosilicate gel. The high conductivity of 0.065 S/cm with a membrane containing 60 wt$\%$ of the gel was obtained at $60^{circ}C$ at $90\%$ relative humidity.