Sol-gel ionic conductors based on nanocomposite ureasil have been studied by attenuated total reflection infrared spectroscopy, time-resolved fluorescence probing, and direct current conductivity. Gels were obtained by acetic acid-catalyzed solvolysis under ambient conditions. IR measurements have shown that acetic acid by itself cannot lead to gelation. Gelation is attained with help from ambient humidity. However, acetic acid solvolysis regulates gel evolution by formation of intermediate products, such as silicon ester and Si-O-Si oligomers. Fluorescence probing and conductivity measurements helped determine the right concentration of acetic acid in the sol to obtain gels with an optimal ionic conductivity. Fluorescence probing has also revealed that ionic conductivity is favored when gels are made of short-polyether-chain ureasil.