Cyclic voltammetry and degradation of dimethylphthalate (DMP) revealed that the iron-substituted heteropolytungstate anion PW11O39Fe(III)(H2O)(4-) is an excellent indirect cathodic oxidative electrocatalyst in the presence of H2O2. PW11O39Fe(III)(H2O)(4-) can electrocatalyze the reduction of H2O2 to hydroxyl radicals via an inner-sphere electron transfer mechanism, which cause oxidative decomposition of DMP. Almost complete DMP removal and ca. 30% mineralization were obtained in less than 120 min in a mixed phosphate solution at pH 6.86 containing 0.1 mM DMP. MS analyses of the intermediates and final products suggested that glyoxal, oxalic acid and acetic acid are the main ring-opening products, besides some unstable hydroxylated aromatic intermediates. The effects of added H2O2 concentration, applied cathodic potential and DMP initial concentration on the degradation of DMP were also investigated. A concentration of 1.0 mM H2O2 and cathodic potential of -0.3 V were optimal conditions for DMP degradation in our experiments. At higher initial DMP concentrations degradation also occurred, but at a slower decay rate compared to lower initial concentrations. The present system thus represents a possible method to use PW11O39Fe(III)(H2O)(4-) as an indirect cathodic oxidative electrocatalyst in water and wastewater treatment. (C) 2008 Elsevier Ltd. All rights reserved.