The kinetics of 2,6-dimethylaniline degradation by Fenton process, electro-Fenton process and photoelectro-Fenton process was investigated. This study attempted to eliminate the potential interferences from intermediates by making a kinetics comparison of Fenton, electro-Fenton and photoelectro-Fenton methods through use initial rate techniques during the first 10 min of the reaction. Exactly how the initial concentration of 2,6-dimethylaniline, ferrous ions and hydrogen peroxide affects 2,6-dimethylaniline degradation was also examined. Experimental results indicate that the 2,6-dimethylaniline degradation in the photoelectro-Fenton process is superior to the ordinary Fenton and electro-Fenton processes. Additionally, for 100% removal of 1 mM 2,6-dimethylaniline, the supplementation of 1 mM of ferrous ion, 20 mM of hydrogen peroxide, current density at 15.89 A m(-2) and 12 UVA lamps at pH 2 was necessary. The overall rate equations for 2,6-dimethylaniline degradation by Fenton, electro-Fenton and photoelectro-Fenton processes were proposed as well. (C) 2011 Elsevier B.V. All rights reserved.