Potentiodynamic and impedance spectroscopy measurements were performed on ARMCO iron, steels (C30, C40, C50), cast iron and graphite electrodes in a bath of industrial composition: CrO3 250 g dm(-3), H2SO4 2.5 g dm(-3). Attention focused on the electrochemical reactions occurring before the start of the chromium deposition. The electrochemical evidence is markedly affected by the chemical nature of the cathode. This is rationalized by proposing a reaction mechanism involving the formation, depending on the chemical nature of the substrate, of a passive adsorbed film consisting of mixed chromium and iron oxides. Moreover, the proposed overall scheme accounts for the presence of periodic current oscillations observed both in potentiodynamic and potentiostatic curves. In close agreement, impedance spectra show negative loops when measured at the corresponding potentials.