For the present study, Bi2O3–B2O3–TeO2 glass system is doped with Fe2O3 to determine its effect on the various properties of the system. Six samples of compositions 35 Bi2O3-40 B2O3-(25-x) TeO2-x Fe2O3 mol %, where x = (0, 0.1, 0.5, 1, 1.5, 2 mol %), are prepared via the melt quenching technique and their physical, thermal, optical, radiation shielding and elastic properties investigated. Raman spectra reveals that the glass network is comprised of BO3, BO4, TeO4 and BiO6 structural units which are disrupted by Fe, acting as a network modifier. XRD patterns confirmed the amorphous nature of the samples. EPR spectra reveal that dopant iron is present in Fe3+ state, at various spins, in the glass network system. Optical absorption measurements (UV-VIS) show that increasing Fe2O3 concentration decreases optical band gap energies which in turn increase refractive index, polarizability and optical basicity of the samples. Metallization criterion indicates that the synthesized glass system non-metallic nature slightly decreases with increasing dopant concentration. Bandgap energy decreased with doping, indicating a decrease in the disorder in the glass network system. Decreases in density and cross-link density were observed with doping whilst increases in molar volume, oxygen molar volume and oxygen packing density occurred. An increase in Hruby's parameter indicates that the thermal stability and glass-forming ability of the samples increased with doping. Elastic moduli increased with doping, increasing the stiffness and damage resistance of the samples. Doping causes a slight decrease in radiation shielding ability; however, radiation shielding ability remains greater than that of concrete.