The present work deals with the fabrication of Bi2O3-CdO-TeO2 glasses using the melt quenching technique. XRD determines the amorphous nature, while the FTIR technique provides information about the molecular vibrations present in a sample. To understand the optical properties of the glass, UV–Vis absorption spectra in the 200–800 nm range and Tauc's plot method to determine the indirect allowed band gap energies are used. The band gap energy decreases as the concentration of Bi2O3 is increasing. Additionally, Monte Carlo (MC) simulation technique has been used to assess the linear attenuation coefficient (μ). The evaluation demonstrates an improvement in μ by 12% and 7%, respectively at 0.15 MeV and 0.662 MeV with increasing the Bi2O3 concentration from 45 mol% to 60 mol%. The half-value thickness (Δ0.5) and lead equivalent thickness (Δeq) of the fabricated samples marginally improved by the minor increase in μ in the mid-gamma energy region. The fabricated samples have applications in the field of gamma-ray shielding.