Despite the increased use of stainless steel for concrete reinforcement in harsh chloride environments, comparatively little is known about the Surface chemistry of these materials in alkaline media simulating concrete pore solutions. This work is concerned with a combined electrochemical and XPS surface analytical investigation on austenitic, ferritic and duplex stainless steels in simple NaOH and more complex alkaline concrete pore solutions. The results show that the passive films on these materials change with immersion time, the ferritic and duplex stainless steels becoming enriched in chromium oxy-hydroxide, the austenitic steel strongly enriched in nickel hydroxide. The composition of the metal layer beneath the Surface film is strongly enriched in nickel and depleted in chromium and iron. The results are discussed with respect to the relation between the Fe(II) content in the films and the open circuit potential (OCP) during exposure, the film growth mechanism and localized corrosion resistance. (C) 2008 Elsevier Ltd. All rights reserved.