This paper presents the effect of Bi2O3 on physical, thermal, structural, mechanical, optical, and radiation shielding properties of borate-based glasses having a composition (60-x)B2O3–25Na2O–13BaO-2Gd2O3-xBi2O3; x = 0, 5, 10, 15, and 20 mol%. XRD analysis confirms the amorphous structure of the prepared glasses. As Bi2O3 content increases from 0 to 20 mol%, density of the glasses increases from 2.729 to 3.896 g/cm3, and molar volume rises from 30.947 to 42.017 cm3/mol. The glass transition temperature (Tg) of the samples decreased with Bi2O3 content. FTIR analysis reveals the presence of BO3, BO4, BiO3, and BiO6 structural units in the prepared glasses. Optical absorption studies indicate a decrease in band gap energy from 3.006 to 2.573 eV for indirect transitions implying non-bridging oxygen atom formation and this inference is supported by both physical and FTIR results. The elastic parameters, derived from Makishima-Mackenzie model decreased with increased Bi2O3 concentration suggesting a reduction in mechanical properties. The mass attenuation coefficient (μm), determined through experimental measurements and using Phy-X/PSD software, yielded closely aligned values. Other shielding parameters such as half-value layer (HVL), mean free path (MFP), and effective atomic number (Zeff) were also calculated. The glass containing 20 mol% Bi2O3 exhibited a significant gamma-ray shielding potential due to its high μm value, (0.1260 cm2/g at 0.511 MeV and 0.0960 cm2/g at 0.662 MeV) and Zeff together with low HVL and MFP. A Comparative analysis of the μm values for the present glasses and that of other glasses containing Bi2O3 is also presented.