This concept focuses on the application of alternating current (AC) and pulsed electrolysis in Atom Transfer Radical Polymerization (ATRP) for polymer synthesis. AC electrolysis, which oscillates between reduction and oxidation, can be tuned to increase selectivity for a specific reaction pathway, minimize side reactions, and improve product selectivity and reagent conversion. Pulsed electrolysis can also be used to sustain electrochemical reactions in ATRP. The challenges and limitations associated with AC electrolysis are discussed along with an outlook on future developments in polymer synthesis and related applications. A concise overview of recent developments in electro-organic synthesis using AC electrolysis will be provided.