Alternating current electrolysis has emerged as a promising technique for addressing challenging redox reactions that are otherwise difficult or impossible for direct current electrolysis. Under mild and transition-metal-free reaction conditions, a general electrochemical denitrative cyclization of nitroarenes was developed to access various cyclic sulfone-containing derivatives of biological significance. The key to success lies in the facile manipulation of multiple redox events upon rapid alternating polarity switching to enhance the selectivity and efficiency.