Glyphosate, one of the organophosphate herbicides, has been widely used in the word. The removal of glyphosate was comparatively investigated by MnO2 oxidation, electrochemical oxidation, and electrochemically assisted MnO2 oxidation (electro-MnO2) processes. The effects of MnO2 dosage, current density, and solution pH on glyphosate removal and Mn2+ release were examined. The results indicated that the removal of glyphosate by MnO2 oxidation favored acidic pH conditions and a large portion of Mn2+ ions were released from MnO2. With the electro-MnO2 process using RuO2/TiO2 coated titanium mesh as both anode and cathode, glyphosate removal was significantly promoted and most of the released Mn2+ ions were oxidatively reverted to MnO2, which in turn enhanced the removal of glyphosate. Solution pH exerted an insignificant effect on glyphosate removal in the electro-MnO2 process. Major reaction intermediates including sarcosine, glycine, and PO43- were indentified in the initial phase of the MnO2 oxidation and electro-MnO2 processes. Glycine was further decomposed to glycolic acid and NH3-N in the MnO2 oxidation process; in contrast, glycine was oxidized into oxamic acid, glycolic acid and N-contained intermediates, and N-contained intermediates could be finally oxidized into acetic acid, NH3-N and NO3--N in the electro-MnO2 process. Crown Copyright (c) 2013 Published by Elsevier B.V. All rights reserved.