A study of the spectroscopic properties, as well as polarizability and optical basicity of TeO2–B2O3 glasses doped with CuO using density, XRD, and UV–Vis analysis, is presented in this paper. The TeO2–B2O3 – CuO glasses are fabricated using the melt-quenching method. The glasses proved to be amorphous in nature from the XRD which was confirmed by the UV–Vis spectra. The peak observed in the pattern of the 0% CuO sample represents the presence of a crystalline phase of α-TeO2 and/or γ-TeO2. Important optical and physical parameters are discussed such as the refractive index (2.318–2.378), metallization criterion (0.4069–0.3919), optical basicity (0.7995–0.8057), electronic polarizability (0.2358–0.2410), linear dielectric susceptibility (0.3480–0.3704 esu), and third order non-linear dielectric susceptibility (1.466 ×1012–1.882 ×1012 esu). Based on the refractive index, metallization criterion, electronic polarizability, optical basicity, and dielectric susceptibility values, the glasses could present great potential applications in fiber optics and laser applications.