© 2020 Elsevier Ltd and Techna Group S.r.l. We investigated photoluminescence (PL), scintillation and thermally-stimulated luminescence (TSL) properties of BaCaBO3F doped with different concentrations of Eu (0, 0.1, 1.0, and 10.0%) to develop phosphor materials for radiation measurement. The Eu-doped samples showed emissions with several sharp peaks due to the 4f-4f transitions of Eu3+ in PL and scintillation while no emission peak was observed in the undoped sample. The decay time constants of the Eu-doped samples in PL and scintillation were about 1.16–1.20 ms and 0.75–1.10 ms, respectively. In addition, the Eu-doped samples showed TSL due to the 4f-4f transitions of Eu3+. The thermal activation energies of the Eu-doped samples were calculated by TSL isothermal analysis, and the analysis suggested that eleven trapping centers with different activation energies involved in TSL might exist in the Eu-doped samples.