The electrochemical properties of self-assembled alkanethiol monolayers on polycrystalline gold electrodes were studied by means of cyclic voltammetry (CV). These films were functionalized by covalent coupling of the o-phenylenediamine (o-PDA) monomer molecules to the alkanethiol monomolecular him, such as to form the centers for further electropolymerization reaction on the surface of the film. The rationale behind this a pp roach was to form the molecular 'wires' of conducting polymer with their structure imposed by the molecular organization of a monolayer and by the covalent linkage of the monomer molecules. (C) 2000 Elsevier Science Ltd. All rights reserved.