Herein, various aspects on the optical, structural, and radiation shielding characteristics of the synthesized glasses doped with Fe2O3 via melt-quenching technique in the system (30-x)BaO-30TiO(2)-40SiO(2)-xFe(2)O(3) (0 < x < 6) were studied. To verify the amorphous nature of the prepared glasses, XRD was performed. Physical properties like density (rho) and oxygen packing density (OPD), revealed their enhanced values within the ranges of 3.5312-4.4135 g/cm(3) and 75.7678-96.7366 g-atom/l. However, the molar volume (V-m) of the fabricated glasses was found to be in decreasing order from 30.3559 to 23.7759 cm(3)/mol respectively. Further insight into the molecular structure was performed via FTIR and Raman spectroscopies which showed the formation of different bonding such as Si-O-Si, Ti-O, and Si-O-Ti along with non-bridging oxygens (NBOs). However, UV-visible spectroscopic results showed the indirect energy band gap (E-g(ind)) decreases from 3.922 to 3.502 eV with increasing the content of Fe2O3 while the refractive index (eta), and optical dielectric constant (epsilon) were found to be in an increasing range of 2.185-2.274 and 4.774-5.169. Further, to determine the elemental distribution and their corresponding electronic states of a tentative glass sample (BTS6F), X-ray photoelectron spectroscopy (XPS) was carried out. In order to study the radiation shielding properties of all the fabricated glasses, the Phy-X/PSD software across a spectrum of energies from 0.015 to 15 MeV was successfully executed. Among all the glasses, the glass BTS6F demonstrates superior gamma-radiation shielding capabilities along with effective optical properties. Therefore, this glass sample can be used for optoelectronics and radiation shielding applications.