A novel route in the synthesis of Al-MCM-41 and Al-MCM-48, using tetraethoxysilane (TEOS) and sodium aluminate (NaAlO2) as Si and Al source has been obtained. The effect of surfactant nature and the synthesis conditions such as surfactant/Si ratio and hydrothermal treatment time on the formed mesostructure regularity has been studied. Different methods of template removal have also been evaluated. The samples were characterized by X-ray diffraction, nitrogen physisorption, FT-IR, and solid-state MAS NMR spectroscopy.