This paper reports a comparative study on the anodic oxidation of 2.51 of 50 mg l(-1) TOC of formic, oxalic, acetic, pyruvic or maleic acid in 0.1 M Na2SO4 solutions of pH 3.0 with and without 1.0 mM Fe3+ as catalyst in the dark or under solar irradiation. Experiments have been performed with a batch recirculation flow plant containing a one-compartment filter-press electrolytic reactor equipped with a 20 cm(2) boron-doped diamond (BDD) anode and a 20 cm(2) stainless steel cathode, and coupled to a solar photoreactor. This system gradually accumulates H2O2 from dimerization of hydroxyl radical ((OH)-O-center dot) formed at the anode surface from water oxidation. Carboxylic acids in direct anodic oxidation are mainly oxidized by direct charge transfer and/or (OH)-O-center dot produced on BDD, while their Fe(III) complexes formed in presence of Fe3+ can also react with (OH)-O-center dot produced from Fenton reaction between regenerated Fe2+ with electrosynthesized H2O2 and/or photo-Fenton reaction. Fast photolysis of Fe(III)-oxalate and Fe(III)-pyruvate complexes under the action of sunlight also takes place. Chemical and photochemical trials of the same solutions have been made to better clarify the role of the different catalysts. Solar photoassisted anodic oxidation in presence of Fe3+ strongly accelerates the removal of all carboxylic acids in comparison with direct anodic oxidation, except for acetic acid that is removed at similar rate in both cases. This novel electrochemical advanced oxidation process allows more rapid mineralization of formic, oxalic and maleic acids, without any significant effect on the conversion of acetic acid into CO2. The synergistic action of Fe3+ and sunlight in anodic oxidation can then be useful for wastewater remediation when oxalic and formic acids are formed as ultimate carboxylic acids of organic pollutants, but its performance is expected to strongly decay in the case of generation of persistent acetic acid during the degradation process. (C) 2009 Elsevier B.V. All rights reserved.