Transient electric fields of up to 1.5 V were generated during the high temperature oxidation of pure metals (Mg, Al, Ti, Zr, Hf, Cr, Mn, Fe, Co, and Ni) either by gaseous oxygen or by solid peroxides or perchlorates. These time-varying fields are most probably due to ion formation and motion in and behind the moving high temperature reaction zone, which creates an electric double layer within individual particles. The shape and magnitude of the induced temporal electric signal depends upon the reactant properties, mode of the front propagation, and mobility of the ions formed. Unsteady combustion front propagation (occurring during the oxidation of Mg, Al, and Nb) generates an oscillatory electrical signal. Metals belonging to the same group in the periodic table (Ti, Zr, and Hf; Ni and Co) and whose products have the same oxidation state generate qualitatively similar electrical signals. The sign and magnitude of the transient electric potential generated during metal oxidation by perchlorates or peroxides are dominated by the chemoionization processes involved in the decomposition of a solid oxidizer. © 2001 The Electrochemical Society. All rights reserved.