1-Dodecylpyrrole (PyCH3) and 12-(pyrrol-l-yl)dodecane-l-thiol (PySH) films have been successfully electrochemically polymerised on electrode from acetonitrile solutions containing the monomer and the lithium perchlorate as supporting electrolyte. The electrochemical study of the polymer growth has been carried out by cyclic voltammetry (CV) detecting the nickel dissolution during electropolymerisation. Several surface spectroscopic and microscopic techniques have been used to characterize the surface in term of chemical composition and polymer topography. The presence of unbound and unoxidised thiol groups at the PPySH surface has been evidenced together with a very strong adhesion to the nickel substrate. Furthermore, N-substituted pyrrole derivatives exhibited some corrosion protection properties in neutral NaCl medium, (c) 2007 Elsevier Ltd. All rights reserved.