A glass sample series was fabricated via melt quenching at 1100 °C according to the chemical formula 4Al2O3-12Na2O-(18-X)SiO2-(64-X)B2O3-(2+2X)Bi2O3 (where X=2, 4, 6, and 8 mol%) to evaluate the role of Bi2O3 substitution for SiO2 and B2O3 on the prepared glass samples' physical, optical, and gamma-ray shielding characteristics. A 6 to 18 mol% Bi2O3 content increase enhances the glass samples' density by 26.12%. The samples' UV-Vis absorption spectra was detected via a UV-Vis spectrophotometer over the 190–1100 nm wavelength interval. The examination of optical properties confirms decreased optical band gap between 3.25–3.02 eV for direct transition while it decrease between 3.03–2.65 eV for indirect transition when the Bi2O3 partially substitutes B2O3 and Si2O decreases glass formers. Additionally, the increase in Bi2O3 concentration within the glass network enhances the γ-ray shielding performance, as confirmed by the Phy-X/PSD program and Monte Carlo simulation. The 6 to 18 mol% Bi2O3 content increase enhances the glass samples' γ-ray interaction cross-sections, while the linear attenuation coefficient increases by 43.44%, 26.61%, and 60.49% at the 0.6, 1.5, and 10 MeV γ-ray energies, respectively.