Sulfonyl　fluorides　have　widespread　applications　in　many　fields.　In　particular,　their　unique　biological　activity　has　drawn　considerable　research　interest　in　the　context　of　chemical　biology　and　drug　discovery　in　the　past　years.　Therefore,　new　and　efficient　methods　for　the　synthesis　of　sulfonyl　fluorides　are　highly　in　demand.　In　contrast　to　extensive　studies　on　FSO2+-type　reagents,　a　radical　fluorosulfonylation　reaction　with　a　fluorosulfonyl　radical　(FSO2.)　remains　elusive　so　far,　probably　owing　to　its　instability　and　difficulty　in　generation.　Herein,　the　development　of　the　first　radical　fluorosulfonylation　of　alkenes　based　on　FSO2　radicals　generated　under　photoredox　conditions　is　reported.　This　radical　approach　provides　a　new　and　general　access　to　alkenyl　sulfonyl　fluorides,　including　structures　that　would　otherwise　be　challenging　to　synthesize　with　previously　established　cross-coupling　methods.　Moreover,　extension　to　the　late-stage　fluorosulfonylation　of　natural　products　is　also　demonstrated.　©　2020　Wiley-VCH　GmbH