The presented work investigates the structural and radiation attenuation properties of modified barium lithium bismuth vanadium borate glasses with varying compositions of B₂O₃, Li₂O, BaO, Bi₂O₃, and V₂O₅. The glasses were fabricated using the melt quenching method, and their physical, structural, and shielding characteristics were systematically analyzed. Fourier transform infrared spectroscopy (FTIR) revealed distinct vibrational modes associated with BO₃, BO₄, Bi-O, and V-O structural units, indicating significant network modifications with increasing Bi₂O₃ content. Density and molar volume measurements demonstrated a direct correlation with compositional changes, while the packing density and free volume provided insights into the structural compactness and ion mobility. Radiation shielding performance was evaluated across a broad photon energy range (0.015–15 MeV), with calculation of key parameters such as the mass attenuation coefficient (MAC), linear attenuation coefficient (LAC), half-value layer (HVL), and effective atomic number (Zₑff). The results showed enhanced shielding efficiency at higher Bi₂O₃ concentrations, particularly near the Bi K-edge (0.1 MeV), where the photoelectric effect (PE) dominated. The sample with 45 mol% Bi₂O₃ exhibited the highest shielding effectiveness, attributed to the high atomic number and density of bismuth. Conversely, the inclusion of V₂O₅ reduced shielding performance, highlighting the critical role of composition optimization. These findings underscore the potential of bismuth-rich borate glasses as effective, non-toxic alternatives for radiation shielding applications in medical, nuclear, and industrial settings. The study provides a foundation for tailoring glass properties to meet specific shielding requirements while maintaining structural integrity.