Molecular assemblies of organothiol molecules on polycrystalline copper surfaces are a well known process to confer them specific organizational and protective properties. In this paper, an original and promising approach is considered through an electro-assisted adsorption process via a cathodic polarization of the copper substrate. Spectroscopic characterizations (PM-IRRAS. XPS) and electrochemical studies (CV, LSV, cathodic desorption, SECM) highlight and confirm the benefits brought by this methodology in terms of resulting SAMs features and considerable savings of preparation time. In addition to normal alkylthiols with a monopod anchoring group, alkyldithiocarboxylic acid and alkyldithiol monolayers - both bipodal -are characterized with the prospect of forming either easier to remove or more adherent films, respectively. (C) 2011 Elsevier Ltd. All rights reserved.