Sulfonyl　fluorides　have　attracted　considerable　and　growing　research　interests　from　various　disciplines,　which　raises　a　high　demand　for　novel　and　effective　methods　to　access　this　class　of　compounds.　Radical　flurosulfonylation　is　recently　emerging　as　a　promising　approach　for　the　synthesis　of　sulfonyl　fluorides.　However,　the　scope　of　applicable　substrate　and　reaction　types　are　severely　restricted　by　limited　known　radical　reagents.　Here,　we　introduce　a　solid　state,　redox-active　type　of　fluorosulfonyl　radical　reagents,　1-fluorosulfonyl　2-aryl　benzoimidazolium　triflate　(FABI)　salts,　which　enable　the　radical　fluorosulfonylation　of　olefins　under　photoredox　conditions.　In　comparison　with　the　known　radical　precursor,　gaseous　FSO2Cl,　FABI　salts　are　bench-stable,　easy　to　handle,　affording　high　yields　in　the　radical　fluorosulfonylation　of　olefins　with　before　challenging　substrates.　The　advantage　of　FABIs　is　further　demonstrated　in　the　development　of　an　alkoxyl-fluorosulfonyl　difunctionalization　reaction　of　olefins,　which　forges　a　facile　access　to　useful　beta-alkoxyl　sulfonyl　fluorides　and　related　compounds,　and　would　thus　benefit　the　related　study　in　the　context　of　chemical　biology　and　drug　discovery　in　the　future.　Sulfonyl　fluorides　are　compounds　with　potential　application　in　chemical　biology　and　drug　discovery,　but　their　preparation　can　be　challenging.　Here,　the　authors　present　a　type　of　bench-stable　fluorosulfonyl　radical　reagents　that　enable　radical　fluorosulfonylation　reactions　via　photoredox　catalysis.