It was studied in this research the nuclear radiation shielding behavior and structure properties of the four glass samples which were composed of (80-x) B2O3-10Na2O-10K2O-xBi2O3 (x=0, 15, 30, 45 mol%) and were prepared using the melt-quenching technique. The studied samples were symbolized as Bi0.0, Bi0.15, Bi0.30, and Bi0.45 according to the Bi2O3 content values. The nuclear shielding properties have been calculated by the Phy-X/PSD program in the photon energy from 0.015 to 15 MeV. The results indicated that the values of mass attenuation coefficient (MAC) ranged from 4.2 to 88.5 cm2/g, linear attenuation coefficient (LAC) values ranged from 8.99 to 429.99 cm-1, half-value layer (HVL) values decreased from 0.077 to 0.002 cm, tenth value layer (TVL) values decreased from 1.570 to 0.020 cm, mean free path (MFP) values decreased from 0.682 to 0.009 cm, effective atomic number (Zeff) values ranged from 12.9 to 77.5, effective electron density (Neff) values ranged from 5.00 × 1023 to 8.60×1023 electrons/g, atomic and electron cross-sections (ACS and ECS) values ranged from 1.09 × 10-22 to 7.98 × 10-21 cm2/g and from 8.47 × 10-24 to 1.03 × 10-22 cm2/g respectively. The effective neutron removal cross-section (ƩR) values for prepared samples were also calculated. The results indicated that the addition of bismuth oxide leads to an improvement in the nuclear shielding properties of the prepared glass and showed that the sample Bi0.45 has the best nuclear shielding properties than concrete and commercial glasses.