New glass systems of bismuth borate with various concentrations of cadmium oxide are prepared based on the melt‐quenching method. The X‐ray diffraction (XRD) reveals a fully amorphous structure of the prepared glasses (S1–S4), and the UV–vis results display good transparency (>50%) in the visible and near‐UV region. In addition, the radiation shielding properties (mass attenuation coefficient, half‐value layer, tenth value layer, mean free path, effective atomic number, and electron density) of the new glass system are determined at selected energies experimentally and by using MCNP5 simulation code and XCOM computer program. Based on the calculated relative difference, the obtained values from MCNP5 and XCOM are in good agreement with the experimental data. The mean free path of the current systems (particularly S4) shows optimistic results when compared with the barite and chalcocite concretes.