Employing　aerobic　polymerization　approaches　is　a　feasible　strategy　to　fundamentally　address　the　phenomenon　of　oxygen　blocked　polymerization.　A　reversible　addition-fragmentation　chain　transfer　(RAFT)　polymerization　system　(COF/H2O/O2)　using　a　photobionic　enzyme　was　successfully　constructed,　in　which　a　TFPPy-azine-COF　serves　as　an　enzyme-like　workstation,　oxygen　and　H2O　are　substrates,　and　light　is　an　externally　tunable　stimulus　to　generate　hydroxyl　radicals　for　catalysing　the　RAFT　polymerization.　Molecularly　diverse　COFs　provide　a　well-documented　heterogeneous　platform　for　the　design　and　development　of　recyclable　oxygen-catalyzed　RAFT　polymerization　systems.　©　2022　The　Royal　Society　of　Chemistry.