Solutions of 30 mg L-1 of the herbicide atrazine have been degraded by environmentally friendly electrochemical advanced oxidation processes (EAOPs) such as anodic oxidation (AO), electro-Fenton (EF), and photoelectro-Fenton (PEF) using a small open and cylindrical cell with a boron-doped diamond (BDD) anode. AO has been carried out either with a stainless steel cathode or an O-2 diffusion cathode able to generate H2O2. Hydroxyl radicals ((OH)-O-center dot) formed at the BDD surface in all EAOPs and in the bulk from Fenton's reaction between added Fe2+ and electrogenerated H2O2 in EF and PEP are the main oxidants. All treatments yielded almost overall mineralization, although the rate for total organic carbon (TOC) removal is limited by the oxidation of persistent byproducts with center dot OH at the BDD surface. In AO, TOC abatement is enhanced by parallel electrochemical reduction of organics at the stainless steel cathode, while in PEF, it also increases from additional photolysis of intermediates by UVA light under the synergistic action of (OH)-O-center dot in the bulk. The effect of current and pH on the degradative behavior of EAOPs has been examined to determine their optimum values. Atrazine decay always follows a pseudo-first-order reaction, being more rapidly destroyed from (OH)-O-center dot in the bulk than at the BDD surface. Aromatic intermediates such as desethylatrazine, desethyldesisopropylatrazine, and cyanuric acid and short linear carboxylic acids such as formic, oxalic, and oxamic have been identified and quantified by reversed-phase and ion-exclusion HPLC, respectively. Released inorganic ions such as Cl-, NO3-, and NH4+ have been followed by ionic chromatography.