Reversible charge transfer on boron doped diamond (BDD) electrodes was studied using cyclic voltammetry and electrochemical impedance spectroscopy. Polycrystalline diamond films of 5 mum thickness with 200 and 3000ppm boron content were prepared by chemical vapour deposition on niobium substrate. The samples were mounted in a Teflon holder and used as rotating disk electrodes (RDE) with rotation frequencies between 0 and 4000 rpm. The electrochemical measurements were carried out in aqueous electrolyte solutions of 0.5 M Na2SO4 + 5mM K-3[Fe(CN)(6)]/K-4[Fe(CN)(6)] and 0.1 M KCl + 5 mM [Ru(NH3)(6)]Cl-2/[Ru(NH3)(6)]Cl-3. The electrochemical redox behaviour of the BDD electrodes was found to differ significantly from that of an active Pt electrode. The deviations are indicated by a large peak potential difference and a shift of the peak potentials in cyclic voltammograms with increasing sweep rate. At rotating electrodes lower limiting current densities are found and the impedance diagrams exhibit an additional capacitive impedance element at high frequencies. The results are described quantitatively by an impedance model which is based on partial blocking of the diamond surface. (C) 2003 Elsevier Ltd. All rights reserved.