This study aims to perform multidirectional characterizations on nuclear shielding efficiencies on some bismuth-based glasses. Accordingly, the γattenuation coefficients for xBi2O3-(75-x)B2O3–25Li2O (x = 0, 10, 20, 30, 40, 50, 60 the 70 mol%) were widely evaluated using simulations and theoretical methods. Linear attenuation coefficient (LAC) of the glasses was obtained by the Monte Carlo general-purpose simulation code FLUKA and compared with the XCOM database up to 15 MeV. Moreover, LAC values have been utilized to evaluate related parameters like mass attenuation coefficient (MAC), total molecular cross-section (σt), total atomic cross-section (σa), half-value layer (HVL), total electronic cross-section (σe), mean free path (MFP), effective atomic number (Zeff), and effective electron density (Neff). The results noted that the XCOM and FLUKA data of the shielding parameters are in great agreement. Relatively higher density (5.818 g/cm3), greater LAC, MAC, Zeff, and lower HVL, MFP values are achieved for 70Bi2O3-5B2O3–25Li2O glass. Accordingly, this glass sample is a better gamma shield.