A manganese/copper co-catalyzed electrochemical Wacker–Tsuji-type oxidation of aryl-substituted alkenes has been developed. The process involves the use of 5 mol % MnBr₂ and 7.5 mol % CuCl₂, in 4:1 acetonitrile/water in an undivided cell at 60 °C, with 2.8 V constant applied potential. α-Aryl ketones are formed in moderate to excellent yields, with the advantages of avoidance of palladium as a catalyst and any external chemical oxidant in an easily operated, cost-effective procedure.