The oxidation products formed on ferritic/martensitic (F/M) steel exposed to oxygen-saturated lead-bismuth eutectic (LBE) at 550 °C for 1000 h were investigated using various characterizations. The results indicate that the corrosion products consist of three distinct layers from the inside to the outside: the inner oxidation zone (IOZ), a middle oxide layer, and the growth front facing LBE. In the IOZ, although O has penetrated the entire oxidation layer, the martensite laths and ferrite grains remain visible. However, significant segregation of Cr and O along the laths and grain boundaries has occurred, resulting in the formation of strip-shaped Cr2O3 particles. In the matrix adjacent to the IOZ, Cr atoms have segregated at the grain boundaries and martensite laths, forming Cr-rich regions, while O atoms have not yet infiltrated. During the growth of Fe3O4 grains, the priority formed strip-shaped Cr2O3 particles are pushed toward the corrosion front until they detach from the F/M steel and disperse into the LBE, resulting in nearly pure Fe3O4 grains in the middle layer. The gradient three-layer structure of the oxidation product is closely associated with the segregation of Cr and the gradient distribution of oxygen partial pressure (PO2).