This paper deals with the electrochemical reactivity of boron doped diamond (BDD) electrodes. A comparative study has been carried out to show the influence of the presence of graphitic micro-domains upon the surface of these films. Those graphitic domains are sometimes present on as-grown boron doped diamond electrodes. The effect of doping a pure Csp(3) diamond electrode is established by highly oriented pyrolytic graphite (HOPG) abrasion onto the diamond surface. In order to establish the effect of doping on a pure Csp(3) diamond electrode, the amount of graphitic domains was increased by means of HOPG crystals grafted onto the BDD surface. Indeed that method allows the enrichment of the Csp(2) contribution of the electrode. The presence of graphitic domains can be correlatively associated with the presence of kinetically active redox sites. The electrochemical reactivity of boron doped diamond electrodes shows a distribution of kinetic constants on the whole surface of the electrode corresponding to different active sites. In this paper, we have studied by cyclic voltammetry and electrochemical impedance spectroscopy the kinetics parameters of the ferri/ferrocyanide redox couple in KCl electrolyte. A method is proposed to diagnose the presence of graphitic domains on diamond electrodes, and an electrochemical "pulse cleaning" procedure is proposed to remove them. (c) 2004 Elsevier Ltd. All rights reserved.