Recently,　radical　fluorosulfonylation　is　emerging　as　an　appealing　approach　for　the　synthesis　of　sulfonyl　fluorides,　which　are　highly　in　demand　in　various　disciplines,　particularly　in　chemical　biology　and　drug　discovery.　Here,　we　report　the　first　establishment　of　radical　hydro-fluorosulfonylation　of　alkenes,　which　is　enabled　by　using　1-fluorosulfonyl　2-aryl　benzoimidazolium　(FABI)　as　an　effective　redox-active　radical　precursor.　This　method　provides　a　new　and　facile　approach　for　the　synthesis　of　aliphatic　sulfonyl　fluorides　from　unactivated　alkenes,　and　can　be　further　applied　to　the　late-stage　modifications　of　natural　products　and　peptides,　as　well　as　ligation　of　drugs　in　combination　with　click　chemistry.　Remarkably,　this　system　could　enable　the　radical　hydro-fluorosulfonylation　of　alkynes,　affording　valuable　alkenylsulfonyl　fluoride　products　with　a　rare,　high　Z-selectivity,　which　are　normally　less　stable　and　more　challenging　to　synthesize　in　comparison　with　the　E-configured　products.　©　2022　Wiley-VCH　GmbH.