Nano-scale chemical inhomogeneity in surface oxide films formed on a V- and N-containing martensite stainless steel and tempering heating induced changes are investigated by a combination of synchrotron- based hard X-ray Photoelectron emission spectroscopy (HAXPES) and microscopy (HAXPEEM) as well as microscopic X-ray absorption spectroscopy (μ-XAS) techniques. The results reveal the inhomogeneity in the oxide films on the micron-sized Cr2N- and VN-type particles, while the inhomogeneity on the martensite matrix phase exists due to localised formation of nano-sized tempering nitride particles at 600 °C. The oxide film formed on Cr2N-type particles is rich in Cr2O3 compared with that on the martensite matrix and VN-type particles. With the increase of tempering temperature, Cr2O3 formation is faster for the oxidation of Cr in the martensite matrix than the oxidation of Cr nitride-rich particles.