A combined experimental and first-principle study on the oxidation mechanism of super austenitic stainless steel S32654 at 900 °C for a short time period (1, 3, and 5 h) in air is presented. The samples exhibit excellent oxidation resistance because of the initial and gradual formation of the denser Fe- and Cr-rich layer with increasing oxidation time. Meanwhile, the Mo-rich layer gradually forms because of the Mo diffusion, which results in the formation of the oxide layer with two distinct regions: an inner Fe- and Cr-rich layer and an outer Mo-rich layer. Density functional theory is applied to investigate the diffusion behaviour of Mo atom in the Fe-Cr-Ni/Cr 2O 3 interface and the effects of alloying elements (Fe, Ni, and Mn) on the Mo diffusion. The Mo originating from the alloy matrix tends to diffuse into the Cr 2O 3 part, thereby resulting in the formation of the continuous Mo-rich layer, which is consistent with the experimental behaviour. Moreover, the introduction of Ni to the Cr 2O 3 part can promote the Mo diffusion and the formation of the Mo-rich oxide layer, whereas Fe and Mn can hinder the Mo diffusion. The calculated results provide a microcosmic explanation of the experimental results.