An Fe–44Ni nanocrystalline (NC) alloy thin film was prepared through electrodeposition. The relation between the microstructure and corrosion behavior of the NC film was investigated using electrochemical methods and chemical analysis approaches. The results show that the NC film is composed of a face-centered cubic phase (γ-(Fe,Ni)) and a body-centered cubic phase (α-(Fe,Ni)) when it is annealed at temperatures less than 400℃. The corrosion resistance increases with the increase in grain size, and the corresponding corrosion process is controlled by oxygen reduction. The NC films annealed at 500℃ and 600℃ do not exhibit the same pattern, although their grain sizes are considerably large. This result is attributed to the existence of an anodic phase, Fe_0.947Ni_0.054, in these films. Under this condition, the related corrosion process is synthetically controlled by anodic dissolution and depolarization.