AbstractCe‐doped silica films with various Ce concentrations were prepared via ion beam sputtering (IBS) and ion implantation. The samples containing 1.46 at.% Ce were annealed at various temperatures from 500 to 1100 °C in air ambient and a separate sample with the same Ce concentration was annealed at 1100 °C in nitrogen gas. The Ce‐related photoluminescence (PL) was observed for the samples and found to be sensitive to the Ce concentrations, annealing conditions and fabricating processes. The PL intensity increases with increasing Ce concentrations from 0.09 to 0.58 at.%, and the concentration‐induced quenching effect occurred as the Ce concentrations reached 1.46 at.%. Also, the PL intensity is enhanced as the samples were annealed at various temperatures from 500 to 900 °C in air ambient, then decreases remarkably as the annealing temperature reached 1100 °C. In addition, compared with the sample annealed in air, the PL intensity can be enhanced for the sample annealed in nitrogen gas. Distinctive PL spectra were found for the samples prepared via different processes.