This work is focused on the study of the role of several conductive-diamond characteristics (boron doping, Sp(3)/Sp(2) ratio, diamond-layer thickness) on the performance of the electrolysis of enrofloxacin (as model complex-organic pollutant). Commercial lots provided by an important conductive-diamond manufacturing company have been used. Results show that enrofloxacin electrooxidation is strongly influenced by the conductive-diamond characteristics; particularly the ratio diamond/graphite carbon was found one of the most significant parameters in this process: the higher the content in diamond-carbon the greater the TOC and COD decays in the bulk electrolyses. These results have been interpreted in terms of the oxidation mechanism involved. High graphite content favours direct oxidation of the pollutant on the electrode surface and leads to the formation of many intermediates. On contrary, high diamond content seems to favour the complete oxidation of the organic to carbon dioxide, thanks to the contribution of the oxidants (hydroxyl radicals and electrogenerated reagents) present in a region close to the electrode surface. Likewise, the oxidation rate seems to be improved with increase in the concentration of boron and decrease in the thickness of the substrate layer. (C) 2009 Elsevier B.V. All rights reserved.