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The synthesized glass system with a composition of (80-x) TeO2-10P2O5-10Nb2O5-xKCl mol% (where x = 5, 10, 15, 20, and 25) was successfully fabricated. The density (ρ) and molar volume (Vm) have been calculated. The investigated glasses were characterized using different analysis methods (differential thermal analysis (DTA) and UV-VIS-NIR spectroscopy). The radiation shielding effectiveness of the synthesized glass system was evaluated using different shielding parameters, such as mass and linear attenuation coefficients (MAC, LAC), half-value layer (HVL), mean free path (MFP), effective atomic number (Zeff), and effective electron number (Neff). The results showed that with the increasing potassium chloride (KCl) concentration and decreasing tellurium oxide (TeO2) concentration, the density, refractive index, Urbach energy (Eu), and glass transition temperature (Tg) decreased, while the optical energy gap (Eopt) and thermal stability increased. As the KCl concentration increases, the values of MAC, LAC, and Zeff increase in the following order: TPNK5 % > TPNK10 % > TPNK15 % > TPNK20 % > TPNK25 %. Additionally, the shielding effectiveness of TPNK glass system showed good performance compared with some standard materials. The synthesized glass with a minimum KCl content has both good shielding effectiveness and good optical properties, in addition to reasonable thermal stability, which makes it suitable for shielding and optical applications.