A new series of tellurite glass-ceramic was prepared for potential utilization in the radiation shielding field. The thermal features of parent glasses were assessed to choose the best heat treatment technique. The morphological and structural properties of glass ceramics were investigated by scanning electron microscope (SEM), X-ray diffraction (XRD), and Fourier transform infrared (FTIR). The UV absorption was utilized to calculate the optical features of glass ceramics. The shielding properties were computed based on the Phy-X software. The transformation of glasses to glass ceramics enhanced the density of all glass ceramics. XRD results exhibited an orthorhombic BaTeO3 crystalline phase for the TMSB0 and TMSB5 samples. It is proved that the monoclinic molybdenum tellurium oxide (Mo5TeO16) crystalline phase for TMSB10, TMSB15, and TMSB20 samples. Also, the change in crystalline phase resulted from adding MoO3 instead of TeO2. SEM results affirmed the role of MoO3 in improving the structure of glass ceramics. The thermal stability and weight loss of TMSB20 samples are higher than other glasses. Also, the adding MoO3 led to a slight enhancement in the radiation shielding properties of the prepared samples. Data indicate that adding MoO3 to the glasses enhanced the glass-ceramic samples' thermal, structural, and radiation protection properties.