The results of this study will help in the development of a novel glass composition containing Yb2O3 concentrations. The impacts of substitution of B2O3/Yb2O3 on the physical, optical, and radiation shielding properties for the B2O3-PbF2-CaO-Li2O glass system were investigated. The glass system was fabricated under melting and annealing temperatures of 1050 °C and 400 °C using the melting quenching method. The density of the fabricated samples ranged between 4.33 g cm−3 to 4.60 g cm−3 with enrichment of the Yb3+ content between 0–8.21 wt%, respectively. Moreover, the enrichment of the Yb3+ ions shows an enhancement in the optical properties of the fabricated glasses where the direct energy band gap enhanced between 4.192 and 4.188 eV and the Urbach energy raised from 0.52 to 0.59 eV with raising the Yb3+ concentrations. The Yb3+ incrementation shows an enhancement in the γ- ray shielding properties where the linear attenuation coefficient was raised by factors of 15%, 6%, and 5% at γ-ray energies of 0.015 MeV, 0.662 MeV, and 1.173 MeV, respectively. Due to the tiny Yb3+ concentration added to the fabricated glass system, the results showed a small increase in the linear attenuation coefficient values in the low γ-ray energy but no significant enhancement in the intermediate and high-ray energies.