A　metal-free　synthesis　of　useful　β-keto　sulfonyl　fluorides　has　been　established　via　radical　fluorosulfonylation　of　ketone-derived　vinyl　acetates　under　photoredox　organocatalysis　by　using　1-fluorosulfonyl　benzoimidazolium　(FABI)　as　the　fluorosulfonyl　radical　source　and　oxygen-doped　anthanthrene　(ODA)　as　the　photocatalyst.　A　series　of　aryl　and　alkyl　β-keto　sulfonyl　fluorides　as　well　as　cyclic　analogues　can　be　readily　obtained　in　moderate　to　high　yields　from　widely　available　ketone　starting　materials.　©　2022.　Thieme.　All　rights　reserved.