<p>This work examined the physical, dielectric, and gamma-ray shielding properties of the (65-<i>x</i>) P₂O₅-15 Li₂O-15ZnO-5Bi₂O₃-<i>x</i>Sb₂O₃ glass system in relation to Sb₂O₃. The density of glass specimens rises rapidly as Sb₂O₃ replaces P₂O₅. A little shift in the FTIR principal bands is observed upon the addition of Sb₂O₃, and this shift is directly linked to the phosphate network depolymerizing, which changes the P-O-P bond length. In the frequency spanning from 50 to 5&#xa0;MHz, the dielectric spectroscopy of specimens of glass was examined as a function of frequency. Up to 2.0&#xa0;mol%, the dielectric constant falls as Sb₂O₃ concentration rises and increases beyond that point. The XCOM and the Phy-X/PSD software were utilized to determine the glass mean free path, which included the energy range of 0.01-10&#xa0;MeV. Similar outcomes were obtained with both methods. Furthermore, mean free path, buildup factors, and transmission factors were computed to determine the glass samples’ shielding efficiency. As the Sb₂O₃ concentration in mol.% rose, the radiation shielding properties in the samples under investigation showed a significant improvement, with an order of Sb-4.0 &gt; Sb-3.0 &gt; Sb-2.0 &gt; Sb-1.0 &gt; Sb-0.0 observed at all photon energies. These results demonstrate how very promising the examined glasses are as materials for radiation shielding. Addition of Sb₂O₃ to the zinc bismuth phosphate glass system alters all optical parameters, including the real part, <i>ε</i>1, and imaginary part, <i>ε</i>₂, of the dielectric constant, extinction coefficient (<i>k</i>), and refractive index (<i>n</i>). There is strong transmittance throughout the visible light band and high reflection within the ultraviolet, as indicated by the transmittance (<i>T</i>) as well as reflectance (<i>R</i>) fluctuating with wavelength (<i>λ</i>).</p>