This work presents the synthesis and preparation of a new glass system described by the equation of (70-x) B2O3–5TeO2 –20SrCO3–5ZnO –xBi2O3, x = 0, 1, 5, 10, and 15 mol. %, using the melt quenching technique at a melting temperature of 1100 °C. The photon-shielding characteristics mainly the linear attenuation coefficient (LAC) of the prepared glass samples were evaluated using Monte Carlo (MC) simulation N-particle transport code (MCNP-5) at gamma-ray energy extended from 59 keV to 1408 keV emitted by the radioisotopes Am-241, Ba-133, Cs-137, Co-60, Na-22, and Eu-152. Furthermore, we observed that the Bi2O3 content of the glasses had a significantly stronger impact on the LAC at 59 and 356 keV. The study of the lead equivalent thickness shows that the performance of fabricated glass sample with 15 mol.% of Bi2O3 is four times less than the performance of pure lead at low gamma photon energy while it is enhanced and became two times lower the perforce of pure lead at high energy. Therefore, the fabricated glasses special sample with 15 mol.% of Bi2O3 has good shielding properties in low, intermediate, and high energy intervals.