This paper studies the photosensitive effect of cerium oxide on the precipitation of Ag nanoparticles after femtosecond laser irradiating into silicate glass and successive annealing. Spectroscopy analysis and diffraction efficiency measurements show that the introduction of cerium oxide may increase the concentration of Ag atoms in the femtosecond laser-irradiated regions resulting from the photoreduction reaction Ce3+ + Ag+→ Ce4+ + Ag0 via multiphoton excitation. These results promote the aggregation of Ag nanoparticles during the annealing process. It is also found that different concentrations of cerium oxide may influence the Ag nanoparticle precipitation in the corresponding glass.