Electrophotocatalytic Radical Cyclizations

Cyclization reactions are pivotal for constructing cyclic scaffolds in pharmaceuticals, natural products, and functional materials. The emerging electrophotocatalytic cyclization synergistically merges the unique activation modes of photoexcitation with the precise electron‐transfer control offered by electrochemistry, mitigating the inherent limitations of standalone photocatalysis and electrocatalysis. Specifically, it overcomes the constrained redox window of photocatalysis and the mass transport issues of electrocatalysis, enabling net‐oxidative cyclizations under mild and external oxidant‐free conditions with H 2 as the byproduct. This review summarizes recent advances in electrophotocatalytic radical cyclizations, categorized by substrates (alkenes, alkynes, and non‐alkene/alkyne scaffolds). Reaction mechanisms, characteristics, scopes, and key innovations are discussed, highlighting the distinctive reactivities and selectivities unlocked by this synergistic approach. The current challenges and future perspectives in this rapidly evolving field are also outlined.