The present investigation examined TeO2–MeO3 glasses with different compositions for their ability to absorb γ-rays using the Phy-X and FLUKA Code, respectively. The study covered energies ranging from 0.015 to 15 MeV, where several parameters such as effective atomic number (Zeff), free path mean (GMFP), mass attenuation coefficient (GMAC), macroscopic cross-section (GLAC), and half-value levels were analyzed (GHVL). Glass composite composed of 80% TeO2 and 20% MoO3 was found to have the lowest GLAC content among the tested samples. GHVL = 0.055 cm was the half-value of the 80TeO2–20MoO3 glasses when they were subjected to 80 keV gamma-rays. It is anticipated that the GMFP of the investigated materials ranges from 0.004 to 0.005 cm when subjected to 100 keV gamma-rays. It was said that the increase in Zeff may be attributed to an increased quantity of electrons that were accessible for interaction with photons, resulting in a decreased probability of gamma rays passing through the shielding material. The cumulative impact of these findings demonstrates that specific glass compositions, particularly those that include Tellurium, have the potential to be used as excellent radiation shielding materials. These materials are becoming more important for providing efficient radiation protection in various industries and applications, including medical imaging, nuclear power, and space exploration.