Composition 55SiO2-30B2O3-(x)Li2O-(15-x)Y2O3 (x = 00, 05, 10, 15) are synthesized using melt-quench technique at higher temperature (1550 °C). As-synthesized samples are sintered to form the crystalline phases at different temperature range, i.e., 800 °C and 850 °C. The density (2.40–1.57 g/cc) and molecular weight (87.79–58.40 g/mol) of samples are decreased with increasing Li2O content. The crystallinity of heat-treated glasses was confirmed by using XRD technique. As the concentration of Y2O3 is replaced by Li2O, the optical bandgap (3.79–3.41 eV) and urbach tail (0.31–0.28 eV) are decreased, while, refractive index (n) is showing increasing trend (2.33–2.42). The dielectric constant of YL- samples lies from (22–55) with losses (2–18) at room temperature. The activation energy is decreased due to conduction phenomena occurred in glass-matrix. In this research, results claimed that the prepared glass-ceramics can be applied in optoelectronics application.