The purpose of the study detailed in this paper is to investigate the evolution of microstructural defects in the Fe‐9Cr binary alloy induced by isochronal annealing from 373 to 1223 K. Positron annihilation lifetime spectroscopy (PALS), Doppler broadening spectroscopy (DBS), positron annihilation lifetime calculation, and transmission electron microscope (TEM) are used to analyze and characterize the change of defect concentration, defect type and the micro‐morphology in the Fe‐9Cr alloy as a function of the annealing temperature. The experimental results showed that, a large number of vacancies and dislocations were found to exist in the untreated Fe‐9Cr alloy. The monovacancy (186.2 ps) in the Fe‐9Cr alloy migrated during annealing from room temperature to 573 K. The annealing temperature at 773 K produce aggregation of dislocations and the formation of dislocation networks, as well as their heterogeneous distribution. When the temperature is further increased to 1073 K, most of the vacancies and dislocations are recovered and a bcc‐fcc phase transmition occurred in Fe‐9Cr model alloy. The dislocation density is continuous decreased with the increase of annealing temperature, the recovery is obvious from 773 K annealing to 1073 K annealing in Fe‐9Cr alloy.