The degradation of herbicides 4-chlorophenoxyacetic acid (4-CPA), 4-chloro-2-methylphenoxyacetic acid (MCPA), 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) in aqueous medium of pH 3.0 has been comparatively studied by anodic oxidation and electro-Fenton using a boron-doped diamond (BDD) anode. All solutions are totally mineralized by electro-Fenton, even at low current, being the process more efficient with 1 mM Fe2+ as catalyst. This is due to the production of large amounts of oxidant hydroxyl radical (OH.) on the BDD surface by water oxidation and from Fenton's reaction between added Fe2+ and H2O2 electrogenerated at the O-2-diffusion cathode. The herbicide solutions are also completely depolluted by anodic oxidation. Although a quicker degradation is found at the first stages of electro-Fenton, similar times are required for achieving overall mineralization in both methods. The decay kinetics of all herbicides always follows a pseudo first-order reaction. Reversed-phase chromatography allows detecting 4-chlorophenol, 4-chloro-o-cresol, 2,4-dichlorophenol and 2,4,5-trichlorophenol as primary aromatic intermediates of 4-CPA, MCPA, 2,4-D and 2,4,5-T, respectively. Dechlorination of these products gives Cl-, which is slowly oxidized on BDD. Ion-exclusion chromatography reveals the presence of persistent oxalic acid in electro-Fenton by formation of Fe3+-oxalato complexes, which are slowly destroyed by OH. adsorbed on BDD. In anodic oxidation, oxalic acid is mineralized practically at the same rate as generated. (C) 2004 Elsevier Ltd. All rights reserved.