The lithium-calcium-borate (LiCaBO3) glass co-doped with Ce3+ and Sm3+ ions were successfully fabricated by the conventional melt quenching method. Annealing heat at 710 °C for 2 or 4 h formed the nanocrystals in the glass matrix. The X-ray diffraction patterns have proved the formation of the nanocrystals in materials. The appearance of these nanocrystals changed the glass lattice structure as well as the physical and optical properties of the material. The radiative properties of the LiCaBO3 glass and glass ceramics were analyzed within the framework of Judd-Ofelt theory. The thermoluminescence (TL) properties of the materials were studied by analyzing the glow curve and the TL spectra. The application potential of the materials in the field of dosimetry was proposed based on the investigation results of the parameters such as TL response to irradiation dose, fading rates, and the standard deviation.