This study reported a novel and unprecedented photoredox-catalyzed protocol for direct allylic C–H fluorosulfonylation of alkenes with FABI. This mild protocol exhibited excellent compatibility with various functional groups, broad substrate scope, and promising scalability, enabling convenient access to a wide range of allyl sulfonyl fluorides with exceptional regioselectivity. The synthetic robustness of this strategy was further demonstrated by the late-stage functionalization of natural products and their ligation with other drugs via SuFEx chemistry.