Covalent　organic　frameworks　(COFs)　are　promising　heterogeneous　photocatalytic　platforms　based　on　their　structural　designability　and　diversity.　Here,　porphyrin-based　TCPP-TPDA-COF　was　synthesized　and　served　as　photocatalyst　for　the　application　of　oxygen-tolerant　photoelectron/energy　transfer-reversible　addition-fragmentation　chain　transfer　(PET-RAFT)　polymerization　in　the　aqueous　phase　under　visible　light　irradiation.　The　effects　of　catalyst　loading,　electron　sacrificial　agent　dosage,　solvent　type,　light　sources　and　target　polymerization　degrees　(DPs)　on　the　polymerization　behavior　are　discussed,　and　the　intrinsic　mechanisms　of　the　oxygen　tolerance　properties　are　identified　by　the　control　experiments　and　oxygen　monitoring　experiments.　TCPP-TPDA-COF　endows　the　RAFT　protocol　with　efficient　light　availability,　high　light　dependence,　well　controllability　and　compatibility　with　different　families　of　monomers.　Programmable　COFs　provide　a　powerful　avenue　for　further　expansion　of　photocatalyst　candidates　compatible　with　PET-RAFT　processes　under　oxygenated　atmosphere.　©　2022