The melt-quenching technique was used to prepare five samples of antimony (III) oxide (Sb₂O₃) glasses with chemical composition of ySb₂O₃-15CaO-15Li₂O-(70 − x)B₂O₃: y = 0 (Sb0), 1 (Sb1), 3 (Sb3), 5 (Sb5), and 8 (Sb8) mol.%. The physical and optical characteristics and the gamma-radiation protection effectiveness within 0.015–15 MeV photon energy were investigated. XRD patterns for all Sb glasses confirmed their amorphous nature. The density of the Sb glasses was gradually increased from 2.410 g/cm³ to 2.780 g/cm³. Both the optical energy band gap (E_g) and Fermi energy level (E_F) were increased as a function of increasing antimony (III) oxide content in the glass network: E_g = 2.56 eV, 2.58 eV, 2.62 eV, 2.90 eV, and 2.97 eV, and E_F = 3.68 eV, 3.45 eV, 3.69 eV, 3.97 eV, and 3.99 eV for Sb0, Sb1, Sb3, Sb5, and Sb8 glasses, respectively. Insertion of the Sb₂O₃ in the glass matrix enhanced the mass attenuation coefficient (MAC) of the Sb glasses. The highest MAC values were achieved for Sb8 glass, while the lowest MAC values were achieved for Sb0 glass for all photon energy. Generally, the MAC followed the order (Sb8)_MAC > (Sb5)_MAC > (Sb3)_MAC > (Sb1)_MAC > (Sb0)_MAC. In terms of the half-value layer (HVL) parameter, Sb0 glass demonstrated the highest HVL values, while Sb8 glass demonstrated the lowest values. The effective atomic (Z_eff) and electron (N_eff) numbers showed the same trend as (Sb8)Z_eff, N_eff > (Sb5)Z_eff, N_eff > (Sb3)Z_eff, N_eff > (Sb1)Z_eff, N_eff > (Sb0)Z_eff, N_eff. Both the total atomic (ACS) and the total electronic (ECS) cross-sections were enhanced with increasing antimony (III) oxide content in the glass network. In comparison, our findings confirm that the Sb8 sample is superior for radiation protection among all prepared Sb glasses. On the other hand, the Sb glass is better than some commercial radiation shielding materials such as concrete and RS-253-G18 glasses.