Calcium barium orthosilicate (CaBaSiO4) phosphors having different concentrations of Dy3+ were prepared by solid-state reaction method, and phase structure of the sample was identified by X-ray diffraction (XRD) characterization. It is observed that the XRD pattern matched well with JCPDS file No. 48-0210. Thermoluminescence (TL) of the UV-irradiated (254 nm) samples was recorded using routine TL set-up Nucleonix TLD reader with constant heating rate 5 °C s−1. It is found that the sample containing 1 mol% of Dy3+ and exposed for 27 min gives optimum TL intensity at 130.14 °C and shows single TL glow peak. It order to examine the effect of charge compensator ion, Li+ ions are introduced and it is found the incorporation of charge compensator enhances the TL output. Samples having 1 mol% of Dy3+ and 6 mol% of Li+ exposed for 30 min to UV exposure show maximum intensity at 118 °C. It is also observed that temperature corresponding to TL peak varies with varying Li concentration (ranging from 105.76 to 123.88 °C). Samples having 1 mol% of Dy3+ and 6 mol% of Li+ exposed for 30 min to UV exposure were selected for further studies, such as activation energy, order of kinetics and frequency factor, and all these parameters were evaluated using peak shape method.