The authors studied the binding energies of valence electrons of two oxide scales, the atomic percentages of Cr and Mn elements in two oxide films, the work function of two oxide films on bulk nanocrystalline 304 stainless steel (BN-SS304) and conventional polycrystalline 304 stainless steel (CP-SS304). BN-SS304 was prepared by severe rolling technique, and the two oxide films were formed in atmosphere at 900 ℃ for 24 hours oxidation on BN-SS304 and CP-SS304 surfaces. In the two oxide films, Cr and Mn elements exist in the forms of Cr3+, Cr0, Mn4+ and Mn0. The atomic percentage ratios of Cr3+ / (Cr3+ +Cr0) and Mn4+/ (Mn4++Mn0) in the oxide film on BN-SS304 are lower than those in the oxide film on CP-SS304. The interactions of the two oxides and the valence electrons of elements are Mn—O, Cr—O, 3d and 4s of Mn0 and Cr0. The binding energies of the valence electrons in the oxide film on BN-SS304 are larger than those in the oxide film on CP-SS304, the work function of the oxide film on BN-SS304 is 0.07 eV larger than that on CP-SS304.