Using melt-quenching techniques, the glass system 22SiO 2 -23Bi 2 O 3 -37B 2 O 3 -13TiO 2 À ð5 À xÞ LiF-x BaO was prepared. The amorphous status of fabricated samples were established using X-ray diffraction patterns. Differential thermal analysis (glass transition temperature, crystallization temperature, and thermal stability) as well as optical properties (molar refractivity, bandgap, molar polarizability, reflection loss, metallization, electronegativity, and electron polarizability) of these glasses have been investigated. These structural changes influence the thermal properties, as we discovered. Indeed, as BaO levels rise, all the thermal parameters rise as well. With increasing BaO content, density, and refractive index rise. Bandgap energies for direct and indirect transitions reduced as the BaO content increased while Urbach energy increases. This interpretation attributable to the increment in the bond length of Ba-O. This study suggests that the fabricated glasses' optical and thermal characteristics have improved, making them suitable for a variety of applications.