Sol-gel synthesis in self-organized media for silica materials is shown to result in complex silica morphologies. The composition, microstructure, and viscosity of the bicontinuous microemulsion used-the Figure illustrates such a microemulsion (silica and silicic acid are represented in the water phase and TEOS (tetraethoxysilane) in the oil)-are shown to affect profoundly the formation of interconnecting silica frameworks.