This work investigated the effects of barium ions on radiation shielding properties of samarium-doped barium phosphate (SBPS) glasses with the chemical composition of (100 − y)[(50P2O5)–(50-xNa2O)–(xBaO)]–ySm2O3, where x = 20, 25, 30, 35 and 40 mol %. The corresponding samples coded SBPS-1, SBPS-2, SBPS-3, SBPS-4 and SBPS-5, respectively were prepared using the melt quenching technique. Radiation shielding parameters such as mass attenuation coefficient (MAC), linear attenuation coefficient (LAC), half value layer (HVL), effective atomic number (Zeff) and fast neutron removal cross section (ΣR) were computed using Phy-X/PSD and Monte Carlo simulation tools, in the energy range between 0.015 MeV and 15 MeV. The results revealed that mass attenuation coefficient increased significantly from 22.088 cm2/g (SBPS-1) to 43.262 cm2/g (SBPS-5) at 0.015 MeV. Based on these, SBPS-5 glass having the greatest BaO content, exhibited the highest values of MAC, LAC, Zeff, leading to improved gamma-ray shielding performance. Furthermore, the capacity of the glasses in shielding of fast neutrons was assessed using the fast neutron removal cross-section (ΣR) parameter. Results showed that BaO incorporation substantially improved neutron shielding efficiency of (100 − y)[(50P2O5)–(50-xNa2O)–(xBaO)]–ySm2O3)). Notably, SBPS-5 glass revealed higher potential for gamma ray shielding, while SBPS-1 sample exhibits superior neutron shielding features. Therefore, the current glass systems can be utilized in radiation shielding applications. This research recommends further validation works to specifically examine the thermal stabilities of the current glasses, using high radiation doses. Extensive validation of the results using other sophisticated methods is also recommended.