In this work, one high-alumina and low-lithium glass-ceramic was successfully developed. The crystal phase, structure and properties of glass-ceramics were precisely modulated by heat treatment. DSC, XRD, TEM and SEM were used to investigate crystallization behavior and the results show that a high alumina content can refine crystal particles. Additionally, FTIR, SAXS NMR and XPS were used to investigate the effect of heat treatment on structure and its modulation mechanism was systematically analyzed. The findings indicate that crystallinity is positively correlated with the glass network polymerization degree. Moreover, the properties of product were evaluated using Vickers hardness and transmittance tests, revealing that the mechanical properties of glass-ceramics could be improved while maintaining transmittance with appropriate heat treatment. Ultimately, this method of heat treatment to modulate glass-ceramics properties provides valuable guidance for high-performance glass-ceramics development.