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Oxidation behavior of Super304H and HR3C steel in high temperature steam from an ultra-supercritical coal-fired boiler was investigated in this paper. The results showed that the steam oxidized surface of Super304H ware composed of Fe₂O₃, Cr₂O₃ and FeCr₂O₄, the oxide scale had a thickness of 50⁻70 μm. In addition, the steam oxidized surface of HR3C ware composed of Fe₂O₃, the oxide scale was about 20μm in thickness and contained few pitting. The oxidation product layer of the two samples could be divided into two layers, including outer layer enriched O element and Fe element, and inner layer enriched O element and Cr element. Furthermore, oxide scale spalling was observed on the surface of Super304H sample.