By 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 (Tg), crystallization behavior, and thermal stability. With the gradual substitution of Mg by Al, Tg 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 Tg in Mg‐rich region, the steeper rise of Tg 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 Tg 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.