Catastrophic corrosion of iron by oxychlorination in hydrogen chloride gas containing 0–75 vol. % oxygen at 300–800°C has been investigated mainly by means of measurements of weight loss and the amount of sublimates. In pure hydrogen chloride gas, the corrosion behaviour was determined by the formation and sublimation of ferrous chloride. Addition of oxygen to hydrogen chloride gas greatly accelerated corrosion of iron due to the formation and sublimation of a low melting point volatile ferric chloride by oxychlorination reactions.