Magnesium-aluminum oxynitride MgAlON has garnered significant attention in recent years due to its unique properties and potential applications. Herein, we report a systematic study on the synthesis of MgAlON with tunable composition by employing the combustion method. The Al/Al2O3/MgO mixture was combusted in nitrogen gas, and the effects of Al nitriding and oxidation by Mg(ClO4)2on the exothermicity of the mixture, combustion kinetics, and phase composition of combustion products were investigated. Our results demonstrate that the MgAlON lattice parameter can be controlled by varying the AlON/MgAl2O4ratio in the mixture, which corresponds to the MgO content in the combustion products. This work provides a new pathway for tailoring the properties of MgAlON, which may have significant implications in various technological applications. In particular, we reveal the dependence of the MgAlON lattice parameter on the AlON/MgAl2O4ratio. The limitation of the combustion temperature by 1650 °C resulted in obtaining submicron powders with a specific surface area of about 3.8 m/g2.