Chemical pretreatments of polycrystalline electroplated copper surfaces have been performed with n-dodecaneselenol, C12H25SeH, and n-dodecanethiol, C12H25SH. Using XPS and PM-IRRAS as surface analysis techniques and electrochemical methods, the monolayers of n-dodecaneselenol were studied comparatively to those of n-dodecanethiol. A beginning of self-cleaning and reduction of the surface copper oxide layer is evidenced already after 5 min of contact time with both of molecules, while a complete removal of the surface copper oxide is only achieved with n-dodecaneselenol molecules. Both molecules show good blocking properties as well as corrosion inhibition efficiency. Again better properties are noted with the selenol molecule. (c) 2007 Elsevier B.V. All rights reserved.