The presented work sheds light on the impact of CeO2 content and sintering temperatures on the microstructure and physical characteristics of Soda-Lime-Alumino Silicate Glass Ceramics for possible use in dental applications. Samples of nominal composition 45SiO2-15Al2O3-(20-x)NaO2-(20-x)CaO-2xCeO2, (x = 1–5) were successfully synthesized via the sol–gel technique. Synthesized samples were characterized by Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, X-ray diffraction scan (XRD), and Scanning electron microscopy (SEM) supplemented with an EDX and calculate roughness parameters in addition to physical properties such as (density, free volume, oxygen packing density, etc.). XRD reveals that 850 °C is the optimal temperature to transform samples to their corresponding glass–ceramic derivative, leading to the rearrangement of Qn Si in the glass network. The rearrangement was explained through FTIR, Raman, and the surface morphology of samples. In addition, the increased density is attributed to the high compactness of the glass ceramic formed resulting from the addition of CeO2, which improves the durability and hardness of the samples.