A study of photon attenuation and optical properties was performed for (20Bi2O3–60B2O3–(20-y)PbO–yTiO2), where y = 0.0, 1.0, 2.5, 5.0, 7.5, and 10.0 wt%) glassy system. UV–Vis absorption measurements for the glasses in the range of 90–1100 nm wavelengths have been recorded. Based on the absorption spectra, the band gap of optical energy for each glass sample has been evaluated using absorbance spectrum fitting ( E Optical ASF ) and derivative absorbance spectrum fitting ( E Optical DASF ) models and compared with those obtained by Tauc's method. E Optical ASF varies from 2.405 to 2.008 eV, while E Optical DASF takes values from 3.000 to 2.914 eV. Indeed, different optical parameters such as refractive index, molar polarizability, molar refractivity, metallization criterion, dielectric constants, optical transmission, reflection loss, band gap of optical energy-based metallization criterion, and refractive index-based metallization criterion have been evaluated. Moreover, several shielding parameters such as mass attenuation coefficients, linear attenuation coefficient, half-value layer, tenth-value layer, mean free path, effective atomic numbers, and effective electron densities have been evaluated using the WinXCOM program in the energy range 0.010–15 MeV for the prepared glass system. At 1 MeV photon energy, the half value layer for the investigated glasses takes values from 2.03 to 2.15 cm. The results showed that the studied glasses can be applied as candidate for radiation shielding materials according to their coefficients of mass attenuation and HVL values, especially the composition with the highest value of PbO (20 wt%), which introduced good nuclear radiation shielding. [ABSTRACT FROM AUTHOR]