In this study, a novel series of glass networks with varying bismuth and barium contents—B57Bi18, B53Bi22, B49Bi26, and B45Bi30—was fabricated using the melt-quenching technique. The density of the fabricated glass samples was determined using Archimedes’ principle. Key shielding metrics—including the Linear Attenuation Coefficient (LAC), Half-Value Layer (HVL), Tenth-Value Layer (TVL), Mean Free Path (MFP), and Effective Atomic Number (Zeff)—were analyzed over a photon energy range of 0.01 to 15 MeV. Results indicate that higher bismuth content—exemplified by the B45Bi30 composition—enhances shielding performance. At 0.1 MeV, this sample exhibited a notable LAC of 25 cm⁻¹, along with reduced HVL and TVL values, outperforming compositions with lower bismuth concentrations. Zeff analysis indicates that the B45Bi30 composition achieves a Zeff of 75 at low energies, affirming its superior attenuation efficiency. Based on these findings, the B45Bi30 glass sample is identified as a promising candidate for radiation shielding applications, particularly in the photoelectric energy range.