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Alternating current electrolysis (ACE) is an emerging powerful synthetic tool, which principally resembles photoredox catalysis strategies. Its periodically alternating polarity feature allows oxidation and reduction processes to take place on the same electrode surface in a well-controlled manner via the fine-tuning of current frequency along with other reaction parameters. Therefore, many challenging transformations in typical direct electrolysis, including constant current electrolysis or constant potential electrolysis, could be achieved via ACE. The recent advances in the organic synthesis using this emerging technology and its advantages over direct electrolysis are highlighted.