Abstract A new approach to promoting ferric reduction efficiency using electrochemical, photoreduction and photo-assisted electrochemical processes has been developed. The use of UVA irradiation and electric current as electron donors can efficiently initiate a Fenton reaction called the photoelectro-Fenton process. 2,6-Dimethylaniline was the target compound in this study. Parameters including initial pH, ferrous ion dosage, hydrogen peroxide concentration, the electric current applied and the number of UVA lamps used were investigated to evaluate the performance of the photoelectro-Fenton process. The removal efficiencies of 2,6-dimethylaniline, COD, TOC and initial degradation rate were determined in this study. The optimum condition for 1 mM of 2,6-dimethylaniline degradation was achieved when using 1 mM of ferrous ions, 20 mM of hydrogen peroxide at pH 2 and 2 A of electric current applied with four UVA lamps used. The energy cost, reaction mechanism and intermediates identification of 2,6-dimethylaniline degradation have also been determined in this study.