© 2019 Elsevier B.V. We synthesized 0, 0.02, 0.2, 1.0, and 10% Ce3+ doped CaF2–AlF3–AlPO4 glasses; and then, we evaluated their photoluminescence (PL), scintillation and thermally stimulated luminescence (TSL) properties. Depending on the concentration of Ce3+, PL quantum yield (QY) ranged from 15.8 to 62.8%. When the materials were irradiated by X-rays, scintillation was observed with an emission peak around 330 nm due to 5d→4f transitions of Ce3+. The scintillation decay times ranged 14–25 ns. The glasses showed intense TSL, and the glow peak was broad peaking around 100 °C. The 0.2% and 1.0% Ce3+ doped samples demonstrated high sensitivity with a good linearity over 5 orders of magnitude (0.1 mGy–10 Gy).