A mild, operationally convenient, and practical method for the synthesis of synthetically usefulN-arylsulfonylimines fromN-(arylsulfonyl)benzylamines using K2S2O8in the presence of pyridine as a base is reported herein. In addition, a “one-pot” tandem synthesis of pharmaceutically relevantN-heterocycles by the reaction ofN-arylsulfonylimines, generated in situ withortho-substituted anilines is also reported. The key features of the protocol include the use of a green oxidant, a short reaction time (30 min), chromatography-free isolation, scalability, and economical, deliveringN-arylsulfonylimines in excellent yields of up to 96%. While the oxidation ofN-aryl(benzyl)amines toN-arylimines using K2S2O8is reported to be problematic, the oxidation ofN-(arylsulfonyl)benzylamines toN-arylsulfonylimines using K2S2O8has been achieved for the first time. The dual role of the sulfate radical anion (SO4·−), including hydrogen atom abstraction (HAT) and single electron transfer (SET), is proposed to be involved in the plausible reaction mechanism.