Abstract: The Al-Al₂O₃-MgO composites with added aluminum contents of approximately 0wt%, 5wt%, and 10wt%, named as M₁, M₂, and M₃, respectively, were prepared at 1700℃ for 5 h under a flowing N₂ atmosphere using the reaction sintering method. After sintering, the Al-Al₂O₃-MgO composites were characterized and analyzed by X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The results show that specimen M₁ was composed of MgO and MgAl₂O₄. Compared with specimen M₁, specimens M₂ and M₃ possessed MgAlON, and its production increased with increasing aluminum addition. Under an N₂ atmosphere, MgO, Al₂O₃, and Al in the matrix of specimens M₂ and M₃ reacted to form MgAlON and AlN-polytypoids, which combined the particles and the matrix together and imparted the Al-Al₂O₃-MgO composites with a dense structure. The mechanism of MgAlON synthesis is described as follows. Under an N₂ atmosphere, the partial pressure of oxygen is quite low; thus, when the Al-Al₂O₃-MgO composites were soaked at 580℃ for an extended period, aluminum metal was transformed into AlN. With increasing temperature, Al₂O₃ diffused into AlN crystal lattices and formed AlN-polytypoids; however, MgO reacted with Al₂O₃ to form MgAl₂O₄. When the temperature was greater than (1640 ±10)℃, AlN diffused into Al₂O₃ and formed spinel-structured AlON. In situ MgAlON was acquired through a solid-solution reaction between AlON and MgAl₂O₄ at high temperatures because of their similar spinel structures.