Chromium oxide (Cr2O3)-doped borosilicate (BS) glasses were prepared by melt quenching of mechanically alloyed Cr2O3 and BS powders. The structural properties of the BS glass doped with different amounts of Cr2O3 (0.25, 0.5, 0.75, 1, 3, and 5 wt%) were investigated using X-ray diffraction (XRD) and Fourier transform infrared spectroscopy techniques. In addition, the radiation shielding properties of the Cr2O3-doped BS glasses were determined at photon energies in the range of 22.10–59.54 keV using an HPGe detector with a resolution of 182 eV at 5.9 keV. The XRD analyses showed that BS glass samples containing 0–1 wt% Cr2O3 were completely amorphous, whereas at Cr2O3 contents > 1 wt%, eskolaite (Cr2O3) crystal phase was observed. Furthermore, the BS glass sample containing 5 wt% Cr2O3 shielded X and gamma radiations more effectively than other samples. •Chromium oxide (Cr2O3; 0.25–5 wt%) doped glass was prepared by melt quenching.•Borosilicate glass samples containing 0–1 wt% Cr2O3 are completely amorphous.•Radiation shielding properties were determined in the range of 22.10–59.54 keV.•Borosilicate glass with 5 wt% Cr2O3 exhibited good radiation shielding properties.