The copper-doped lithium borate glass as a thermoluminescent (TL) material (100−x) B2O3–xLi2O : Cu2+ (x= 20, 50 and 80 mol%) was prepared by the combustion method. The formation of (100 − x )B2O3–xLi2O : Cu2+ after doping 2, 3 and 5 ppm Cu2+, was characterized by Fourier transform infrared spectroscopy, X-ray diffraction and transmission electron microscopy. The TL characteristics of the synthesized material were studied at different parameters. The synthesized glass 50B2O3–50i2O : Cu2+ with 3 ppm of doped Cu2+, exhibited the superior TL properties than other glasses prepared in the current study. The spin-Hamiltonian parameters were assessed using the electron spin resonance spectra of 50B2O3–50Li2O : Cu2+ doped with 3 ppm Cu2+. The spin-Hamiltonian parameter values in the case of Cu2+ revealed that the ground state of Cu2+ was dx 2–y 2 orbital ( 2 B 1 g ) and the site symmetry around Cu2+ ion was distorted octahedral. TL glow curves were recorded with different heating rates (1, 2, 5, 10, 15, and 20∘C s−1) at the fixed dose 10 × 103 Gy. The results revealed that the glow peak position shifted to higher temperature with heating rate and the heating rate of 10∘C s−1 showed the superior TL response with highest glow peak which is very good for dosimetry purposes.