Electrolytic degradation of dinitrotoluenes (DNTs) and 2,4,6-trinitrotoluene (TNT) in wastewater was conducted by Electro-Fenton's reagents. The batch-wise experiments were carried out to elucidate the influence of various operating variables on the electrolytic behavior, including electrode potential, oxygen dosage, electrolytic temperature, acidity of wastewater and dosage of ferrous ions. It deserves to note that the nitrotoluenes contained could be completely decomposed by Electro-Fenton's reagents, wherein hydrogen peroxide was in situ generated from cathodic reduction of oxygen, supplied mainly by anodic oxidation of water. During the electrochemical process, the influence of electrolytic temperature on the degradation of nitrotoluenes is the most significant, followed by electrode potential, acidity of wastewater and oxygen dosage. Based on the spectra analyzed by gas chromatograph/mass spectrometer (GC/MS), it is proposed that initial denitration of 2,4-DNT and/or 2,6-DNT gives rise to formation of o-mononitrotoluene, which undergoes the cleavage of nitro group into toluene, followed by oxidation of methyl group to benzoic acid and subsequent decarboxylation. It is believed that the electrolytic method established is potentially applied to dispose wastewater from toluene nitration processes in practice. (C) 2009 Elsevier B.V. All rights reserved.