Novel composite gel electrolytes were prepared using self-assembled organogels as scaffolds. Mixing silica with the low-molecular-weight poly(ethylene glycol) (PEG)-based electrolytes resulted in precipitation due to significant aggregation of silica. However, clear and transparent PEG silica composite gel electrolytes were obtained with 1,3:2,4-dibenzylidene-D-sorbitol (DBS) organogels. The organogels resulted from the formation of DBS nanofibrillar networks in which the diameter sizes of the nanofibrils ranged from 10 to 100 nm, as observed by transmission electron microscopy. These three-dimensional nanofibrillar networks entrapped the silica and prevented its aggregation. The thermal properties, such as gel dissolution and thermal degradation temperatures, of the composite gels significantly increased with increasing silica content, as determined by polarizing optical microscopy and thermogravimetric analysis. The conductivity of the prepared composite gel electrolytes was clearly enhanced by increasing the silica content. The silica was well dispersed along the DBS nanofibrillar networks, establishing homogeneous microstructures and effective contact with other components of the electrolytes, leading to an increase in the conductivity.