The growing demand for radiation-resistant optical glasses for space and nuclear radiation applications has attracted significant research interest. However, radiation-resistant fluorophosphate glasses have been poorly studied. In this work, we report on the tailoring and performance of radiation-resistant fluorophosphate glasses that contained cerium through codoping with Sb2O3 and Bi2O3. The physical properties, optical properties, microstructure, and defects of fluorophosphate glasses were investigated using transmittance measurements, absorption measurements, as well as Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and electron paramagnetic resonance (EPR) spectroscopy. The results showed that the radiation resistance of all codoped fluorophosphate glasses was better than the undoped cerium-containing fluorophosphate glasses after 10–250 krad(Si) irradiation. Especially in glasses doped with Bi2O3, the optical density increment at 385 nm was only 0.1482 after 250 krad(Si) irradiation. The CeO2 prevented the development of phosphate-related oxygen hole center (POHC) defects, whereas further codoping with Bi2O3 suppressed the formation of oxygen hole center (OHC) and POEC defects, reducing the breaking of phosphate chains caused by CeO2. Bi3+ is more likely than Sb3+ to change the valence, affecting the transition equilibrium of intrinsic defects and reducing the concentration of defects produced by irradiation. When codoping with Sb2O3 and Bi2O3, Bi2O3 does not enhance radiation resistance owing to the scission effect of Sb2O3 on the phosphate chain, which is not conducive to the radiation resistance of glasses. This indicates that the cerium-containing fluorophosphate glasses doped with Bi2O3 can effectively suppress the defects caused by irradiation and improve the radiation resistance of the glasses. © 2022 Elsevier Ltd and Techna Group S.r.l.