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Fluoroalkyl sulfones, valued for their stability, accessibility, and structural tunability, have emerged as versatile precursors for radical fluoroalkylation. Herein, we present a photocatalyst\u2010free and straightforward method for direct fluoroalkylation through an EDA complex, utilizing inexpensive iodide anion as an electron donor and fluoroalkyl sulfones as acceptors. Upon visible light irradiation, the EDA complex undergoes single\u2010electron transfer (SET) to generate fluoroalkyl radicals, which subsequently react with a diverse array of silyl enol ethers with high efficiency. The method features mild reaction conditions, broad functional group compatibility, and an extensive substrate scope that encompasses bioactive molecules and sterically demanding architectures. Mechanistic investigations indicate the involvement of an iodide\u2010mediated EDA complex and support the proposed radical\u2010generation pathway. This work establishes a practical and sustainable platform for fluoroalkylation, underscoring the utility of iodide in EDA\u2010based photochemistry and broadening the scope of radical synthetic methods.<\/jats:p>","DOI":"10.1002\/anie.8941062","type":"journal-article","created":{"date-parts":[[2026,7,30]],"date-time":"2026-07-30T16:23:13Z","timestamp":1785428593000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Sulfone Activation Triggered by Iodide Anion for Photoinduced Fluoroalkylations"],"prefix":"10.1002","volume":"65","author":[{"given":"Yu","family":"He","sequence":"first","affiliation":[{"name":"Department of Chemistry University of Science and Technology of China  Hefei Anhui China"},{"name":"State Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences  Shanghai 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