This study demonstrates the promising potential of WO3-doped calcium lithium silicate borate glasses as a multifunctional material with adjustable characteristics for a range of current technological purposes. The melt quenching technique was used for the manufacture of calcium lithium silicate borate glass samples doped with WO3 with a chemical composition of (50-x)B2O3+10SiO2+15CaO+25Li2O + xWO3, where x = 0, 1, 2, 3, and 5 mol%. Raman spectroscopy and UV optical absorption methods were used to investigate the spectroscopic characteristics of glass samples. The dielectric characteristics of the produced glass samples were investigated by broadband dielectric spectroscopy (BDS) measurements. The extremely short-range ordering structural matrices revealed by X-ray diffraction have validated the amorphous nature. The Raman spectra of the calcium lithium silicate borate glass exhibit considerable differences from those of glasses containing WO3. The prepared glass samples exhibited an obvious relationship between the replacement of WO3 and their density and molar volume. As a result of a modification in the structure, the values of packing density (Vp) and oxygen packing density (OPD) decrease as the molar concentration of WO3 increases. The inclusion of WO3 increased the optical absorbance of the synthesized glasses, as demonstrated by UV–Vis optical absorption spectra. According to the dielectric characteristics, the dielectric loss and dielectric constant decrease with frequency, while the AC electrical conductivity exhibits a progressive increase.