The kinetic aspects of the competitive reaction of CO and H2O in the formation of chromia layer on a nickel base alloy at high temperature were studied by thermogravimetry combined to gas phase chromatography. It was shown that competitive adsorption occurred between both molecules and that whatever P-CO/P-H2O ratio, CO mainly reacted in the first instants of oxidation and H2O became the main long-term oxidant species. After an interfacial and diffusion mixed kinetic regime, the long-term oxidation rate was parabolic and did not depend on the water vapor content in the gas phase. The oxidation kinetics was well described by considering that the rate limiting step was the outwards diffusion of interstitial chromium cations in the oxide layer. (C) 2012 Elsevier Ltd. All rights reserved.