Oxidation behaviors of NiAl, Ni3Al, and FeAl under oxygen atmosphere at low pressures were studied by X-ray photoelectron spectroscopy (XPS). Clean surfaces of these aluminides were prepared by fracturing in an ultra high vacuum, and then the fractured surfaces were oxidized by exposing to high-purity oxygen at pressures up to 1.3 Pa without exposing to air. The oxides formed on NiAl and FeAl surfaces were Al2O3, whereas the oxide on Ni3Al was NiAl2O4. Aluminum, nickel, and iron on clean surfaces were oxidized even at a pressure of 1.3 x 10 (6) Pa. The oxidation evolves with an increase in the pressure of oxygen, and further oxidation of aluminum occurs prior to that of nickel or iron. The oxidation behaviors under such oxygen atmosphere were similar to those of the aluminides oxidized in air, and these behaviors could be predicted from thermodynamic consideration. (c) 2008 Elsevier B.V. All rights reserved.