High temperature oxidation of ferritic stainless steel 21Cr-0.6Mo-Nb-Ti was carried out isothermally at 1100 oC under different water vapour content conditions in an electrical furnace. Water vapour does accelerate the formation of oxide scale of stainless steel 21Cr-0.6Mo-Nb-Ti, however, it is not significant. Some oxide grains consist of spinel crystal structure, which should be spinel Manganese Chromite. In dry air atmosphere, the grain of the spinel is more and bigger than that in wet air. No breakaway oxidation occurs in the experiment indicating that 21Cr-0.6Mo-Nb-Ti has very high oxidation resistance, which might be contributed by the formation of MnCr2O4 and compact protective chromia. In addition, continuous silica formed along and accumulated at the oxide metal interface performs like a diffusion barrier.