The primary objective of this study is to explore the relationship between the composition, structure, and thermal characteristics of M-Al-Si-O-N glasses, with M representing sodium (Na), magnesium (Mg), or calcium (Ca). The glasses were prepared by melting in a quartz crucible at 1650 °C and AlN precursor (powder) was utilized as a nitrogen source. The measured thermal properties studied were glass transition temperature (Tg), crystallization temperature (Tc), glass stability, viscosity, and thermal expansion coefficient (α). The findings indicate that increasing the aluminum content leads to higher glass transition, crystallization temperatures, and viscosities. In contrast, fragility values increase with the Al contents, while modifier elements and silicon content influence thermal expansion coefficient values. FTIR analysis revealed that in all glasses, the dominant IR bands are attributed to the presence of Q2 and Q3 silicate units. The effect of Al is observed as a progressive polymerization of the silicate network resulting from the glass-forming role of Al2O3. In most samples, the Q4 silicate mode was also observed, strongly related to the high Al content. Overall, the study shows that the complexity of composition-property correlations where the structural changes affect the properties of Mg/Ca-based oxynitride glasses has potential implications for their use in various technological fields.