In order to improve the protection abilities of (3-mercaptopropy)trimethoxysilane (MPTS) self-assembled monolayers on copper surfaces, mixed monolayers have been formed successfully by successive immersions in MPTS and in n-dodecanethiol (DT). A newly synthesised molecule, (I I mercaptoundecyl)trimethoxysilane (MUTS), has also been employed to form a thicker organic film on copper surfaces and, thereby, enhance the inhibitory action of the coating. The grafting has been confirmed by X-ray photoelectron spectroscopy (XPS), polarization modulation infrared reflection adsorption spectroscopy (PM-IRRAS) and water contact angle. The protective efficiency of each protective organic film has been evidenced by cyclic voltammetry(CV) and polarization curve measurements (CP). It was shown that the MUTS and unhydrolyzed MPTS/DT films exhibited significant corrosion protection properties. (c) 2008 Elsevier Ltd. All rights reserved.