Sulfonyl　fluorides　have　widespread　applications　in　many　fields.　In　particular,　the　increasing　research　interest　on　the　study　of　sulfonyl　fluorides　in　the　context　of　chemical　biology　and　drug　discovery　in　the　past　decade　has　raised　a　high　demand　for　new　and　efficient　methods　for　the　synthesis　of　sulfonyl　fluorides.　Even　though　many　synthetic　routes　have　been　developed　in　recent　years,　the　corresponding　radical　fluorosulfonylation　remains　elusive.　Here,　we　report　our　efforts　toward　this　goal,　and　the　identification　of　sulfuryl　chlorofluoride　(FSO2Cl)　as　an　effective　fluorosulfonyl　radical　precursor,　as　well　as　the　development　of　radical　fluorosulfonylation　of　alkenes　and　radical　trans-chloro/fluorosulfonylation　of　alkynes.