A novel process involving the simultaneous electrochemical oxidation and electrosynthesis of permanganate oxidant has been explored for the treatment of the triazine organic herbicide, atrazine. The electrochemical synthesis of permanganate in neutral pH conditions using low concentration manganese (Mn2+), analogous to levels found in some raw groundwater sources, and their subsequent effect on atrazine degradation were studied in bench-scale experiments. Permanganate synthesis was found to be largely unaffected by the operating current density (10, 40 and 80 mA cm−2) during electrolysis, indicating as mass transport controlled process. Under the same operating conditions, hydroxyl radical mediated oxidation was observed to degrade atrazine from an initial concentration of 9.27 µM (2 mg L−1), to 6.22, 4.88 and 2.36 µM after 120 min of electrolysis for 10, 40 and 80 mA cm−2 conditions. When 55 µM (3.0 mg L−1) Mn2+ was added to the water matrix, atrazine degradation increased, yielding final concentrations of 5.80, 3.66 and 2.17 µM, respectively. Atrazine degradation was found to be accurately described by pseudo-first-order reaction kinetics, with and without the enhanced oxidation by permanganate generation, as the concentration of hydroxyl radicals remained constant and comparatively high throughout electrolysis. Finally, the yielded second-order reaction rate constants of electrochemically generated permanganate, and dosed potassium permanganate, with atrazine were 9.79 and 8.35 M−1 s−1, respectively, whereby the latter degradation mechanism was kinetically limited and the former was under mass transfer control due to an extremely low permanganate-atrazine ratio. Finally, four primary oxidation by-products were observed to form in the reactions, including deethylatrazine, deisopropylatrazine and deethyldeisopropylatrazine.