The initial oxidation of Fe-, Co-, and Ni-based engineering alloys was studied in situ by high-temperature cyclic voltammetry. Measurements were performed at constant temperatures between 500 and 800 degrees C in an electrochemical cell utilizing oxygen ion-conducting yttria-stabilized zirconia as electrolyte and a reference electrode whose potential is determined by the oxygen activity in the ambient gas. The recorded voltammograms show clear current peaks that are associated with the oxidation of the base metal in the investigated alloys. For the Fe- based alloy, multiple peaks are observed, showing oxidation of Fe into different valence oxides. The results indicate that the base metal oxide is formed in the initial oxidation process of these engineering alloys, which may influence long-term high-temperature oxidation resistance of the alloys. (c) 2007 The Electrochemical Society.