Phenylmethylsulfonyl　fluoride　(PMSF)　and　its　analogues　have　been　used　for　decades　as　an　enzyme　inhibitor.　Herein,　we　describe　the　successful　development　of　a　radical　fluorosulfonylmethylation　reaction　under　photoredox　catalysis,　allowing　for　direct　access　to　PMSF　derivatives　from　arenes　and　heteroarenes　via　C-H　functionalization.　This　method　greatly　expands　the　library　of　accessible　PMSF-type　molecules　and　thus　benefits　the　related　study　in　chemical　biology　and　drug　discovery.　By　combination　with　the　SuFEx　click　reaction,　these　PMSF　products　can　be　readily　converted　to　sulfonates　and　sulfonamides,　which　could　overcome　the　low　efficiency　in　the　direct　functionalization　of　arenes　with　the　corresponding　radicals.　In　addition,　an　extension　of　radical　fluorosulfonylmethylation　to　the　functionalization　of　olefins　via　addition,　cyclization,　and　migration　reactions　is　also　demonstrated,　providing　a　facile　synthesis　of　various　alkyl　sulfonyl　fluorides.　©　2024　American　Chemical　Society.