Three-dimensional, mesoporous-cage-type, GaSBA-1 materials with different nSi/NGa ratios have been successfully prepared for the first time by using a low hydrochloric acid to silicon (nHCl/n Si) molar ratio in the synthesis gel by templating with cetyltriethylammonium bromide as the structuredirecting agent in a highly acidic medium. The obtained materials have been unambiguously characterized in detail by several sophisticated techniques including X-ray diffraction (XRD), N 2 adsorption, high-resolution transmission electron microscopy, high-resolution scanning electron microscopy, energy dispersive spectroscopy, elemental mapping, and 29Si magic-angle-spinning NMR spectroscopy. XRD and nitrogen adsorption results reveal that the structures of the GaSBA-1materials resemble that of SBA-1, which possesses a cubic, three-dimensional, cagetype structure with open windows. In addition, the specific surface area and the specific pore volume of the GaSBA-1 materials are much higher than those of the SBA-1 silica, which are very important for the catalytic applications. The amount of Ga cation in the SBA-1 silica framework has been found to play a critical role in controlling the morphology and the pore diameter of the materials. Finally, the catalytic activity in the tert-butylation of phenol with tert-butanol as the alkylating agent has been investigated and the results are compared with those of other mesoporous catalysts such as A1MCM-41, FeMCM-41, FeAl-MCM-41, and FeSBA-1. Moreover, the effect of various reaction parameters such as the reaction temperature, reactant feed ratio, and time-on-stream on the phenol conversion in the tert-butylation of phenol over GaSBA-1 catalysts has been demonstrated. Among the catalysts examined, GaSBA-1 (17), in which the number in the parenthesis denotes the nSi/nGa ratio, showed remarkable activity with a high conversion of phenol and selectivity to 4-tert-butylphenol; it was found to be superior over other mesoporous catalysts used in the study.