Sol-gel syntheses offer a wide range of possibilities for introduction of materials with specific properties (electronic, optic and ion-conductive, etc.) into optically clear matrices. Preparation of silica gel bulk, containing 12-tungstophosphoric acid (WPA) in mesopores, as well as its structural and conduction characteristics are reported. Characteristics of the obtained doped gels depend on the gel preparation, gelation process and the WPA content. According to the obtained results, especially for the high conductivity (sigma similar to 0.1 S/cm), WPA doped silica gel is a promising material for solid electrolytes.