The primary application of radiation shielding is to safeguard against the harmful effects of radiation. This study investigated the addition of thulium oxide (Tm2O3) to a glass system with a composition of 75 TeO2–5 Li2O–10 ZnO– (10-x)Nb2O5. Multiple radiationshielding parameters, including linear and mass attenuation coefficients, half-value layers, mean free paths, atomic and electronic cross-sections, effective atomic numbers, and effective electron density, were evaluated. The study compared the half-value layer values of the new composite to those of well-known radiation-shielding materials, which include ordinary concrete and commercial glass. The addition of Tm2O3 to glass systems efficiently increases the atomic and electronic cross-sections. While all samples had the greatest linear and attenuation coefficients of 201.5–232.84 cm2 /g at 15 keV, the denser glass had the highest mass attenuation coefficient of 42.80 cm2 /g. The shielding effectiveness depends on the phases structure of TeO2 occurred in the prepared glasses.