After starting of using ionizing radiation in many different fields, the scientists focused on to develop protection methods as it is dangers for the human body. Besides time and distance the most important way is shielding of radiation by using effective materials. With this motivation, the present study analyzes the physical, optical, mechanical, and Radiation shielding properties for the B2O3–Li2O glasses. Four different glasses coded as G-1 to G-4 are simulated via MCNPX Monte Carlo code by varying the concentration of the B2O3 + Li2O at 0–15 MeV gamma ray energies. The obtained results reveal that Li2O has a favorable influence on the radiation shielding characteristics of the preferred glass sample. To assess the relation between Li2O concentration in glass and corresponding structural and mechanical changes in candidate glasses, Makishima–Mackenzie theory is applied and mechanical moduli are extracted. The structure and dimensionality of the preferred samples are derived based on the Bergman and Kantor model for fluid and compositions with the help of the fractal bond connectivity. In addition, the longitudinal velocity (VL), transverse velocity (VS), mean velocity (V mean), and acoustic impedance (Zi) related to the glasses are evaluated.