Herein, the effects of oxygen partial pressure (5–20%) and oxidation time (0.5–6 h) on the growth behavior and phase structure of 9% Ni steel oxide layer are studied by means of high‐temperature oxidation experiment, scanning electron microscopy, and X‐ray diffraction. The results show that the inner and outer oxide layers of 9% Ni steel grow opposite to each other along the initial surface direction of the vertical matrix during the high‐temperature oxidation process. From the perspective of the phase, the phase transition of Fe2O3→Fe3O4→FeO mainly undergoes from the outside and the inside, the results of thermodynamic calculations show that <<<0, and the main factor affecting the phase transition is the diffusion concentration of free O and Fe atoms. During the high‐temperature oxidation process of 9% Ni steel, the diffusion of O and Fe atoms along grain boundaries promotes preferential oxidation at these boundaries. The columnar structure formed in the outer oxide layer of 9% Ni steel may be related to the uneven diffusion rate of Fe atoms at different positions at the interface between the inner and outer oxide layers.