Metals and ceramics exposed to high-temperature salt solutions are susceptible to a form of corrosion caused by fused salts accumulating on unprotected surfaces. This article examines the electrochemistry of such hot corrosion processes, focusing on sodium sulfate systems generated by the combustion of fossil fuels. It explains how salt chemistry, including acid/base and oxidizing properties, affects corrosion rates and mechanisms. The article also provides information on electrochemical testing and explains how Pourbaix methods, normally associated with aqueous corrosion, can be used to study fused-salt corrosion.