Amine terminated self-assembled monolayers on gold are widely used as adhesion promoter agent to immobilize nanostructure such as fullerene, proteins and biological cells. The reactivity of the amine function makes difficult the formation of high quality SAMs. Most studies report disordered structure with the presence of oxidized sulphur on the surface. In this work, SAMs of 11-aminoundecyl-1-thiol (NH2-(CH2)(11)-SH) and 2-aminoundecylpropane-1,3-dithiol (NH2-(CH2)(11)-CH-(CH2SH)(2)) have been elaborated on copper substrates, following different protocols (alkalinization during or after the self-assembly). The modification of copper by amine terminated SAMs of thiol and dithiol has been successfully achieved. The best quality of SAMs are obtained when the alkalinization to free amine is carried on after the self-assembly process. Characterizaton of the SAMs are carried out using contact angle goniometry, PM-IRRAS, XPS and CV. (C) 2011 The Electrochemical Society. [DOI: 10.1149/1.3604529] All rights reserved.