The impacts of the Bi2O3/BaO ratio on the microstructure, optical, ligand field, and radiation shielding features of BSrFeBaBi glass matrix. The Bi2O3 content of the BSrFeBaBi glasses was increased from 0 to 20 mol%. The density increased from 3.77 g/cm3 to 5.00 g/cm3 and the molar volume increased from 24.74 cm3/mol to 31.17 cm3/mol with increasing Bi2O3/BaO ratio. The optical analysis confirmed that the transparency of BSrFeBaBi glasses in the visible region is high. Moreover, the presence of Fe cations in the octahedral coordination (FeO6 units) was confirmed. Furthermore, the fundamental absorption edge of BSrFeBaBi glasses shifts towards lower energies with additional Bi2O3/BaO concentrations, confirming the reduced behavior of the optical band gap. Also, ligand field splitting values decreased while Racah parameters increased. The obtained results demonstrate a tendency of the bonds between the Fe ions and their surroundings towards higher degree of ionic nature. Furthermore, the Bi2O3/BaO ratio demonstrated an enhanced radiation shielding behavior. Finally, BSrFeBaBi glasses exhibit favorable attributes for use in the radiation shielding domain due to their efficient radiation shielding features and transparency.