In this study, we developed the phosphate glass doped with CeF3 for scintillator applications. The phosphate glasses, 20Li2O−5Gd2O3–2ZrO2−(73-x) P2O5−xCeF3 were synthesized at different CeF3 concentrations by using the conventional melt-quenching technique. The density, molar volume, transmittance, photoluminescence (PL) and radioluminescence (RL) properties were investigated and quantified. The study found a positive correlation between the concentration of CeF3 with the density values and refractive index of the glass samples. The transmission spectra exhibited a red shift as the level of CeF3 increased. The emission spectra revealed a wide range of wavelengths resulting from the transition between the 5d and 4f transitions of the Ce3+ ion. The maximum intensity of emission for both PL and RL were observed at a concentration of 0.50 mol% CeF3. Moreover, the results of the emission spectra measured under Gd3+ excitation and the PL decay curves of Gd3+ in glass samples showed clearly evidence energy transfer (ET) from Gd3+ to Ce3+. The XPS spectra revealed the existence of phosphorus oxidation states. The XANES analysis revealed the existence of Ce3+ and Ce4+ in all glass samples, as evidenced by the appearance of peaks at approximately 5.728 keV for Ce3+, 5.732 keV and 5.739 keV for Ce4+. The scintillation efficiency of CeF3-doped phosphate glass with a concentration of 0.50 mol% was found to be 60.63% when compared to BGO crystal. Additionally, the decay time is extremely fast, varying from 17.52 to 25.93 ns, which is a critical attribute in the development of radiation detectors. In addition, X-ray imaging was conducted to investigate its potential efficacy in scintillator applications for X-ray imaging. The X-ray imaging investigation had a spatial resolution of 10 lp/mm with an MTF of 0.25. The results suggest that CeF3-doped phosphate glass has the potential to serve as a scintillator in X-ray imaging systems.