The electrochemical behaviour of pure iron and 304L stainless steel in protic organic media has been characterized by determination of current-potential potentiodynamic curves. The media studied was methyl, ethyl, isopropyl, n-butyl and 2-chloroethyl alcohols. The influence of water and chloride ion concentration on the cathodic and anodic electrochemical reactions has been investigated. The presence of water, even at a very low concentration, strongly influences the passivation of iron in protic alcoholic solutions. The kinetics of the oxidation reactions, when water and/or chloride ions were present, are a function of the specific alcohol. This has been interpreted in terms of the different protic and stereo chemistry properties of the alcohols considered.