Modified 9Cr–1Mo steel was oxidized in air at 550 and 750 °C for 25, 100, 250 and 500 h and the oxide scales formed were analysed. The surface morphology and the chemical state of the oxide scales were evaluated using scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), respectively. The different exposure temperatures and time showed significant variations on the surface morphologies, the nature of oxide scale, and oxide constituents. The energy dispersive X-ray spectroscopic (EDS) analysis revealed the segregation of Mn at 750 °C even for short exposure time. Grazing incidence X-ray diffraction (GIXRD) patterns revealed the scales to be enriched with haematite and less intense magnetite peaks. Detailed XPS characterization indicated the presence of mixed oxides of iron (Fe), chromium (Cr) and manganese (Mn) in the oxide scales. The Fe–Cr spinel in the oxide scale offered resistance to oxidation of the steel, whereas Mn–Cr spinel was deleterious in nature as it promoted cracking and formation of blisters.