Photoluminescence and thermally-stimulated luminescence (TSL) characteristics of BaCaBO3F doped with various amounts of Tm were evaluated. The Tm-doped BaCaBO3F showed an emission with a sharp peak around 460 nm originating from the 4f-4f transition of Tm3+ in photoluminescence and scintillation. Their photoluminescence and scintillation decay times for the Tm-doped BaCaBO3F were 0.68–0.73 and 1.28–1.55 ms, respectively. Furthermore, the TSL dynamic range of the glow peaks at 190 °C for the 0.5% Tm-doped BaCaBO3F was from 0.1 mGy to 1000 mGy. Furthermore, the TSL isothermal analysis of the Tm-doped BaCaBO3F suggested that at least 12 different activation energies related to TSL were confirmed. •Tm-doped BaCaBO3F was fabricated by the conventional solid-state reaction.•Tm-doped BaCaBO3F showed efficient TSL with several glow peaks.•Linear TSL dose response was confirmed to be in the dose range from 0.1 to 1000 mGy.