In this work, a comparative study using anodic oxidation, Fenton and electro-Fenton treatments was performed in order to determine the synergic effect for the removal of thiamethoxan. The results determined that electro-Fenton process showed high efficiency in comparison with Fenton or anodic oxidation. After that, this hybrid process was optimized and the influence of iron catalyst concentration and applied current intensity on the degradation and mineralization were evaluated. Degradation profiles were monitored by high performance liquid chromatography (HPLC) being satisfactorily described by pseudo-first order kinetic model. At the optimal experimental conditions (300 mA and 0.2 mM Fe+2), the complete degradation of thiamethoxam was achieved after 10 min. On the other hand, mineralization of thiamethoxam was monitored by total organic carbon (TOC) decay reaching more than 92% of TOC removal after 8 h. Furthermore, a plausible mineralization pathway for the thiamethoxam degradation was proposed based on the identification of by-products such as aromatic intermediates, carboxylic acids and inorganic ions released throughout electro-Fenton process. (C) 2016 Elsevier B.V. All rights reserved.