In this work, we prepared Ca2BO3Cl with various amounts (0.1%–1.0%) of Tm2O3 by conventional solid-state reaction and investigated the dosimeter properties. Scintillation peaks at 370, 455, 470, and 650 nm that were derived from the 4f→4f transition of Tm3+ appeared in the X-ray induced scintillation spectra, and the highest scintillation intensity was detected from the 0.5% Tm2O3-doped Ca2BO3Cl. Furthermore, the Tm2O3-doped Ca2BO3Cl exhibited a thermally-stimulated luminescence (TSL) with a main glow peak at 300 °C, and the fabricated Tm2O3-doped Ca2BO3Cl exhibited a linear response in the 0.1–1000 mGy range. In addition, the TSL spectra confirmed that a final luminescence process for the TSL was the 4f→4f transition of Tm3+. In addition to TSL, optically-stimulated luminescence that was attributable to the 4f→4f transition of Tm3+ was recorded under 520 nm light, and the lowest detectable limit was about 1 mGy.