Heterogeneous　photocatalytic　polymerization　has　emerged　as　a　successful　method　for　the　development　of　greener　reversible　deactivation　radical　polymerization　protocols.　In　this　article,　a　halogen-free　covalent　organic　framework　(1,3,6,8-tetrakis(4-aminophenyl)　pyrene-1,3,6,8-tetrakis(4-formylphenyl)　pyrene-covalent　organic　framework　[TAPPy-TFPPy-COF])　based　on　imine　bonds　was　prepared,　which　mediated　reversible　complexation-mediated　polymerization　of　methacrylates　for　the　synthesis　of　various　polymers　with　controllable　molecular　weight　and　relatively　uniform　distribution　under　white　light-emitting　diode　light　irradiation.　TAPPy-TFPPy-COF　absorbed　the　energy　from　photo　and　was　transformed　to　excited　state　(COF•),　and　then　the　energy　transfer　occurred　between　COF•　and　initiator　2-iodo-2-methylpropionitrile　(CP-I),　which　cleaved　the　carbon-iodine　bond　of　CP-I　to　generate　carbon　radicals,　thereby　initiating　the　polymerization　reaction.　The　density　function　theory　calculation　suggests　that　the　coordination　of　iodine　of　CP-I　with　nitrogen　on　TAPPy-TFPPy-COF　significant　decrease　the　bond　dissociation　energy,　making　the　polymerization　more　efficiency.　The　monomer　conversion　and　reaction　time　showed　a　linear　kinetic　relationship　of　first　order.　The　number　average　molecular　weight　of　the　obtained　polymers　increased　along　with　the　monomer　conversion　rate,　and　in　good　agreement　with　theoretical　molecular　weight,　indicating　a　high　frequency　of　the　activation-deactivation　cycle.　The　obtained　polymer　has　high　chain　end　fidelity,　which　can　be　used　to　synthesize　various　block　copolymers.　This　work　provided　a　new　direction　for　the　development　of　heterogeneous　catalysts　for　reversible　complexation-mediated　polymerization.　©　2022　Elsevier　Ltd