In this paper, the electrochemical oxygen transfer reaction (EOTR) is studied on boron-doped diamond electrodes using simple C, organic compounds (methanol and formic acid). The kinetics of both oxygen evolution (side reaction) and organics oxidation (main reaction) has been investigated using boron-doped diamond microelectrodes-array (BDD MEA). Oxygen evolution, in the high-potential region, takes place with a Tafel slope of 120 mV dec(-1) and zero reaction order with respect to H+. In the presence of organics, a shift of the polarization curves to lower potentials is observed while the Tafel slopes remain close to 120 mV dec(-1). A simplified model of C, organics oxidation is proposed. Both water discharge and organics oxidation are assumed to be fast reactions. The slowest step of the studied EOTR is the anodic discharge of hydroxyl radicals to oxygen. Further in this work, electrolysis of formic acid on boron-doped diamond macroelectrode is presented. In order to achieve 100% current efficiency, electrolysis was carried out under programmed current, in which the current density was adjusted to the limiting value. (c) 2007 Elsevier Ltd. All rights reserved.