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.