Oxyfluoride‐based sodium‐aluminum‐phosphate glasses with a fixed 7 mol% content of Gd2O3 and various amounts of CeF3 were fabricated by the melt quenching process. The fabricated glasses (NAPGCe) were studied by physical, optical, scintillation, and light yield properties. In NAPGCe glasses, intense emission peaks were observed at 312 nm (6P7/2 → 8S7/2) for Gd3+ and 336 nm (5d → 4f) for Ce3+ ions in both photoluminescence (275 and 294 nm) and radioluminescence (X‐ray) spectra. Upon excitation with 275 nm ultraviolet radiation, a decrease in Gd3+ emission and an increase in Ce3+ emission intensity lead to efficient energy transfer (ET) from Gd3+ to Ce3+ ion in NAPGCe glasses. The bi‐exponential function was applied to fit the non‐exponential decay curves of NAPGCe glasses and then calculated their lifetimes in the order of fast (18.25–16.94 ns) and slow (72.99–67.74 ns) decay times. An overall integrated scintillation efficiency of about 67% was estimated for NAPGCe0.10 glass compared to bismuth germanate oxide (BGO:Bi4Ge3O12) crystal. Under 241Am α‐ray (5.5 MeV) source, the light yield of the NAPGCe1.00 glass was obtained by comparing it with a commercial Li‐glass scintillator (GS20), and it was found to be 26 photons MeV−1.