Microfluidic chips and optical elements can be fabricated based on the nonlinear photo-sensitivity in photo–thermo–refractive (PTR) glass by controlling the growth of nanocrystals in the femtosecond (fs) laser–irradiated region. Here, we focus on CeO2 and Sb2 O3 that play important roles in UV irradiation, experimentally investigate the effects of the dopants on the nonlinear photochemical process in PTR glass triggered by fs Gaussian–Bessel beams. The results show that the generation of Ag0 atoms and the Ag nanoparticles can be improved by CeO2 and Sb2 O3 co–doping. Besides, each multivalent ion in PTR glass possibly participates in the electron transfer processes and contributes to the generation of Ag0 atoms. Finally, X–ray diffraction analysis reveals the precipitation of NaF nanocrystals with an average size of 10 to 12 nm after laser irradiation and thermal treatment, which is unrelated to the dopants. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.