Radiation shielding glass is widely used, as it protects people from ionizing radiation while allowing for the observation of irradiated areas. However, the performance of even the best-performing tellurite glass for radiation shielding still falls short compared to traditional radiation shielding materials. The effect of Sm2O3, with a high atomic number and cross section with neutron, on the gamma-ray and neutron shielding properties of a 75TeO2-5Li2O-10ZnO-(10-x)Nb2O5-(x)Sm2O3 glass system is studied in this work. Some critical shielding parameters, including linear attenuation coefficients, half-value thickness, tenth-value layer, and mean free path (MFP), have been calculated with the software Phy-X/PSD. Two kinds of gamma-ray buildup factors, the exposure buildup factor and the energy absorption buildup factor, have been calculated in the range of 0.015 to 15 MeV for depths up to 40 MFP. What’s more, their neutron shielding ability has been evaluated by calculating the neutron total effective removal cross section. It is shown that Sm2O3 promotes the gamma-ray and neutron shielding performance of the 75TeO2-5Li2O-10ZnO-10Nb2O5 glass system. The results indicate that the addition of Sm2O3 can be helpful for the radiation shielding performance of tellurite glass, which provides a practical way for designing glass with ideal shielding properties.