Harnessing Light and Electricity: Hypervalent Iodine‐Induced Radical Fluorination and Fluoroalkylation Reactions

Fluorine incorporation profoundly influences the physicochemical and biological properties of organic molecules, yet conventional fluorination often relies on hazardous reagents and harsh conditions. Recent advances have established hypervalent iodine (HVI) chemistry, combined with light or electricity, as a sustainable platform for radical fluorination and fluoroalkylation under mild, redox‐neutral conditions. This review highlights key developments in photo‐ and electrochemically driven HVI‐mediated transformations, systematically classified by the number of fluorine atoms introduced—mono‐, di‐, and trifluoromethyl/perfluoroalkylation. Emphasis is placed on reaction design, mechanistic insights, and the synergistic role of HVI reagents in enabling efficient, selective, and environmentally benign synthesis of organofluorine compounds.