Sulfonyl　fluorides　have　widespread　applications　in　many　important　fields,　including　ligation　chemistry,　chemical　biology,　and　drug　discovery.　Therefore,　new　methods　to　increase　the　synthetic　efficiency　and　expand　the　available　structures　of　sulfonyl　fluorides　are　highly　in　demand.　Here,　we　introduce　a　new　and　powerful　class　of　sulfonyl　fluoride　hubs,　β-chloro　alkenylsulfonyl　fluorides　(BCASF),　which　can　be　constructed　via　radical　chloro-fluorosulfonyl　difunctionalization　of　alkynes　under　photoredox　conditions.　BCASF　molecules　exhibit　versatile　reactivities　and　well　undergo　a　series　of　transformations　at　the　chloride　site　while　keeping　the　sulfonyl　fluoride　group　intact,　including　reduction,　Suzuki　coupling,　Sonogashira　coupling,　as　well　as　nucleophilic　substitution　with　various　nitrogen,　oxygen,　and　sulfur　nucleophiles.　By　using　BCASF　as　a　synthetic　hub,　a　wide　range　of　sulfonyl　fluorides　becomes　readily　accessible,　such　as　cis　alkenylsulfonyl　fluorides,　dienylsulfonyl　fluorides,　and　ynenylsulfonyl　fluorides,　which　are　challenging　or　even　not　possible　to　synthesize　before　with　the　known　methods.　Moreover,　further　application　of　BCASF　to　the　late-stage　modification　of　peptides　and　drugs　is　also　demonstrated.　©　2021　Wiley-VCH　GmbH