Lithium tetraborate (Li2B4O7) pellets prepared by using water/solution assisted method were synthesized and characterized. Copper was used as doping material in order to enhance the Li2B4O7 thermoluminescent properties. For synthesis heating temperature parameters were defined at 750 °C for 2 hr, followed by 150 °C for another 2 hr. The materials were produced at five different Cu concentrations: 0.02, 0.04, 0.06, 0.08, and 0.1 wt%. The luminescent and morphological characterizations were performed by X-ray diffraction (XRD), Scanning electron microscope (SEM), Photoluminescence (PL), and Ultraviolet-visible spectroscopy (UV-Vis). XRD and SEM analysis of intrinsic and doped materials confirmed the obtained Li2B4O7 structure and show its morphology. XRD patterns of the Li2B4O7 matched a tetragonal crystal structure. Crystals of Li2B4O7 of an average size of 50 nm were obtained. The presence of the copper dopant was confirmed in crystals of Li2B4O7:Cu by SEM-EDS (energy dispersive spectroscopy X-ray). The emission spectrum of Cu doped Li2B4O7 showed a prominent peak at 367 nm, while the main UV-Vis absorption was observed from 240 nm to 300 nm due to Cu+ ion 3d10 → 3d9 4s transitions. The thermoluminescent (TL) response was studied for both γ radiation and X-ray. A 661.7 keV γ radiation using a 137Cs source at doses of 50, 100, 200, 300, 400 and 500 mGy was applied to Li2B4O7:Cu (0.1 wt%) pellets. An X-ray source was used at doses of 600, 800 and 1000 mGy to irradiate pellets of Li2B4O7:Cu (0.02, 0.04, 0.06, 0.08 and 0.1 wt%). A linear TL response was observed for both X-ray and γ radiation. The kinetic parameters were calculated using the peak shape method for the Li2B4O7:Cu (0.1 wt%).