A novel glass system was developed using the melt-quenching technique. The primary aim was to investigate molybdenum-rich compositions (MoO3 > Li2O), with the general formula (69–2x) TeO2–(31+x)–MoO3–xLi2O (where x = 0, 5, 10, and 15 mol%). The physical, structural, thermal, mechanical and radiation shielding properties were evaluated. The synthesized glasses were characterized through their densities, molar volumes, and oxygen packing density, which revealed that the density and molar volume decreased as the amount of Li2O and MoO3 increased in the glass structure, while the oxygen packing density increased as a function of both Li2O and MoO3. Raman spectroscopy was used to analyze the glass structure, which showed a superimposed reduction of all Te units due to the formation of Te–O–Mo and a coordination change from MoO4 to MoO6. The interplay between Li2O and MoO3 has a direct effect on the thermal stability of the glass and reveals that glasses with higher MoO3 content and lower Li2O content exhibit enhanced thermal stability. The mass attenuation coefficient for the synthesized systems varied from 37.07 to 32.38 cm2 g−1 at 0.015 MeV. The fast neutrons removal cross-section exhibits a range from 0.090 to 0.096 cm−1 across all samples, while the thermal neutrons cross section values lie within the interval of 1.22–8.16 cm−1. The glass sample with the highest concentration of TeO2 showed superior values of mass attenuation, and fast neutrons removal cross-section, along with the lowest values of half value layer and mean free path. Nevertheless, the addition of MoO3 and Li2O improved thermal stability and led to adequate radiation protection levels. The results indicate the significant potential of MoO3-rich tellurite materials for shielding against gamma-ray and neutron radiation.