In thin-film applications it is necessary to control film properties such as homogeneity and porosity to obtain high-quality coatings. Electrochemistry can be a very helpful tool since it can provide information about processes taking place at the interface between substrate and coating. Different thin carbon-based coatings were deposited via physical vapour deposition methods and vapour phase polymerization on pure iron substrates: fullerene films, which were modified by an ion bombardment and thin films of poly(p-xylylene), which is a very good insulating polymer. The fihn porosity and stability of the film/substrate system against aqueous corrosion were investigated and compared using cyclic voltammetry. The dependence of porosity and film stability on various deposition process parameters such as film thickness and plasma conditions was measured via the dissolution current density and the open circuit potential shift of the substrate material. It could be shown that the two measurements, current density I-crit. and open circuit potential E-ocp. can provide useful complementary information about film porosity that can lead to a better understanding of the coatings properties and the deposition process as well. (c) 2006 Elsevier B.V. All rights reserved.