In this study, we developed Li₃PO₄–Al(PO₃)₃ glasses doped with different concentrations (0, 0.1, 0.2, 0.5 and 1.0%) of Ce and studied the optical, scintillation and dosimeter properties. The scintillation and photoluminescence (PL) emissions showed an intense emission due to the 5d–4f transitions of Ce³⁺. In addition, the scintillation and PL decay times of Ce³⁺ were obtained for 25–32 and 26–29 ns, respectively. These results were typical for Ce-doped scintillator. Moreover, as a dosimeter property, 0, 0.1, 0.5 and 1.0% Ce-doped glass samples showed thermally stimulated luminescence (TSL) around 150–200 and 350–400°C with a good liner response over 0.5–10 Gy.