AbstractBy using the aerodynamic levitation and laser melting technique to well extend the glass‐forming region into the Mg‐rich and peraluminous regime, a series of magnesium aluminosilicate glasses were prepared to investigate the Mg and Al mixed effects on thermal properties, including glass transition temperature (T_g), crystallization behavior, and thermal stability. With the gradual substitution of Mg by Al, T_g exhibits two types of near‐linear rises with different slopes in two compositional regions separated by r = 0.57, where r is equal to the molar ratio of [Al₂O₃]/([Al₂O₃] + [MgO]). Moreover, when it comes to other properties, that is, crystallization behavior and thermal stability, this critical point precisely appears at the same r = 0.57. Compared to the slower increase of T_g in Mg‐rich region, the steeper rise of T_g in the peraluminous region is mainly ascribed to the step‐by‐step formation of oxygen triclusters driven by Pauling's second rule. Moreover, the occurrence of the critical point for T_g rise at r = 0.57 rather than the theoretical 0.5 can be seen as a proof of the role of Mg cations partly as a network former.