The　advancement　in　the　synthesis　of　functional　polymeric　materials　has　greatly　benefited　from　the　development　of　functionalized　monomers　and　effective　polymerization　methods.　Here,　inspired　by　the　controlled　radical　polymerization　and　the　new　generation　of　click　chemistry,　sulfur(VI)　fluoride　exchange　(SuFEx),　we　introduce　a　SuFExable　vinyl　monomer,　4-vinylbenzenesulfonyl　fluoride　(VBSF),　which　shows　a　good　balance　of　stability　and　reactivity　and　can　readily　undergo　organocatalytic　atom-transfer　radical　polymerization　under　visible　light　with　good　controls　and　high　end-group　fidelity,　while　retaining　the　sulfonyl　fluoride　groups　intact.　Moreover,　poly(VBSF)　can　be　further　modified　with　high　efficiency　via　SuFEx　reactions　with　various　aryl　silyl　ethers,　thus　allowing　a　rapid　construction　of　a　functional　polymer　library　in　a　click　fashion.　©　2023　American　Chemical　Society.　All　rights　reserved.