The gamma-Ga2O3-Al2O3 mixed oxides with a spinel structure were prepared by the solvothermal reaction of gallium acetylacetonate and aluminum isopropoxide in diethylenetriamine. In the crystal structures of the catalysts obtained by the calcination of these mixed oxides, Ga3+ and Al3+ ions preferentially occupied tetrahedral and octahedral sites, respectively. The catalysts with low Ga contents had a unique structure with high surface areas and a concentration gradient of decreasing Ga content from the surface to the bulk. In methane-selective catalytic reduction (SCR) of NO, higher NO conversion to N-2 was attained on the catalyst with high occupation of Ga3+ ions at tetrahedral sites and Al3+ ions at octahedral sites. For the gamma-Ga2O3-Al2O3 mixed oxide with a charged Ga molar content of 0.3 (ST(0.3)), tetrahedral and octahedral sites were solely occupied by Ga3+ and Al3+ ions, respectively, and the catalyst exhibited the highest NO conversion to N-2. Therefore, it was concluded that the active site for methane-SCR of NO is tetrahedral Ga3+ ion and octahedral Al3+ ion, which are linked to each other. Nitrogen monoxide is adsorbed on the isolated hydroxyl group attached to Al3+ ions and then oxidized by O-2 yielding surface nitrate species. Tetrahedral Ga3+ ions work as Lewis acid sites for the activation of methane because of their coordinative unsaturation. The Ga3+ ions in the gamma-Ga2O3-Al2O3 catalyst have a redox property, which plays important roles in both the oxidation of NO to Surface nitrate species and the activation of methane. The most important factor for this catalyst is that the sites for the formation of surface nitrate species reside next to the methane activation sites, which facilitates the reaction between surface nitrate species and the activated species derived from methane, thus mitigating the consumption of methane by simple combustion with O-2. Therefore, ST(0.3), which has the largest number of ensembles of the tetrahedral Ga3+ ions and octahedral Al3+ ions, shows the highest activity for methane-SCR of NO.