A novel one-step synthesis route to ordered mesoporous silica-pillared clay (SPC) with cantonic-anionic mixed-gallery templates has been successfully established. This approach involves the type and formation of surfactant mixture for SPC through intragallery ammonia-catalyzed tetraethoxysilane (TEOS). The formation of a precursor with a micromesoporous framework is a result of TEOS hydrolysis and the presence of surfactant micelles in the gallery regions under ammonia-catalyzed conditions. The type of structure was confirmed by X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and low-temperature N-2 physisorption. Addition of the anionic surfactant resulted in changes of the layered structure and ratio of micropores to mesopores. The formation mechanism of SPC derivatives is proposed.