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　β-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.　©　2022,　The　Author(s).