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This paper presents a comprehensive investigation of borate-based glasses doped with BaO, assessing their physical, structural, optical, and radiation shielding properties through experimental and theoretical analyses. XRD patterns reveal the amorphous nature of the prepared glass samples. Density and molar volume values, and FTIR spectra indicate the impact of BaO concentration on the glass matrix, affecting structural properties. Thermal analysis via TGA/DSC reveals improved thermal properties with the substitution of B 2 O 3 with BaO. UV–visible absorption spectroscopy shows a decrease in energy band gap with rising BaO content, suggesting potential non-bridging oxygen formation. Mass attenuation coefficient (μ m) values exhibit an exponential decay trend with photon energy, influenced by photoelectric absorption, Compton scattering, and pair creation. The glasses prepared had, in general, a better μ m values compared to that of concretes and other glass compositions containing barium oxide. Experimental and theoretical (XCOM) results for mean free path (MFP) and half-value layer (HVL) demonstrate close agreement, validating the accuracy of the experimental data. Both MFP and HVL increase with energy and decrease with BaO addition, emphasizing the potential for these glasses in radiation shielding applications. • Borate based glass samples of the composition (70-x)B 2 O 3 –20Bi 2 O 3 –5ZnO–5WO 3 -xBaO; x = 0, 5, 10, 15 and 20 mol% have been successfully prepared by melt-quenching process. • The addition of BaO in the glass system improves its density, thermal and gamma radiation shielding properties. • The study elucidates structural modifications of borate glasses imparted by the doping of BaO. • Non-toxic and environmentally friendly nature, along with effective shielding behavior, of our prepared glass samples makes it a practical solution for gamma shielding applications. [ABSTRACT FROM AUTHOR]