Glass samples of composition xCeO2–(35–x) Bi2O3–20BaO–45B2O3 (x = 0, 0.25, 0.5, 0.75, 1 and 2 mol%) have been prepared. The studied glasses were named as G0–G5 according to the values of CeO2, respectively. Many properties of the proposed glasses were determined. Both of FTIR and UV–Visible are measured in the range of 400–4000 cm−1 and 200–1100 nm, respectively. The ability of the prepared glass to attenuate gamma-ray was investigated utilizing the newly Phy-X/PSD software. Density of glasses has minor increase as the increase of CeO2, while molar volume decreased from 38.0625 to 35.3803 (cm3/mol). The absorption edge of UV is shifted towards longer wavelength with increasing the concentration of CeO2 whereas a remarkable decrease in bandgap (2.45–2.02 eV) is observed. In addition, the refractive index of studied samples is increased from 2.56 to 2.73 with the increasing the concentration of CeO2 in the studied glasses. There are a change in the structure of studied samples by the addition of Ce ions such as change from BO3 to BO4 groups and formation of BiO6 groups. The MAC values arranged in the order that (G0)MAC > (G1)MAC > (G2)MAC > (G3)MAC > (G4)MAC > (G5)MAC. The G0 glass sample has the highest HVL among all prepared glasses. It is found that Zeff of all prepared glasses has the maximum value at 0.02 meV equal to 78.6436, 78.59407, 78.54402, 78.49343, 78.4423, and 78.23216 for G0–G5, respectively. Therefore, G0 and G5 glasses showed best shielding capacity among several commercial materials. Thus, the prepared glasses introduced themselves as superior candidates for shielding against gamma photons.