A glass in the SiO2–Al2O3–MgO–Na2O system was formulated using a non-conventional silica source and other pure raw materials. The thermal stability and crystallization mechanism have been studied by means of differential scanning calorimetry (DSC). Besides, the glass ability to sintering–crystallization has been examined by optical dilatometry, a non-contact technique allowing the acquisition of dilatometric data in the viscoelastic temperature region. The experimental data were confirmed with theoretical equations. X-ray diffraction and field emission scanning electron microscopy were used to verify the crystallization study and electron scanning microscopy to examine the fired sample microstructures. The prevalent crystallization mechanism has been evaluated from different parameters derived from characteristic temperatures of non-isothermal DSC curves, namely the working range (DTTS), reduced glass transition temperature (Tgr), and the dissimilarity in crystallization temperature (DTp) between fine (< 63 micron) and coarse (fragment) glass samples.