The　photo-induced　reversible　complexation-mediated　radical　polymerization　(photo-induced　RCMP)　has　the　feature　of　energy-saving　and　environmentally　friendly,　which　is　compatible　with　the　sustainable　development　advocated　by　the　world.　To　promote　the　development　of　photo-induced　RCMP,　three　two-dimensional　conjugated　microporous　polymers　(CMPs)　based　on　different　construction　units　were　developed　by　aldehyde-ammonia　condensation　and　used　as　catalysts,　producing　polymethacrylates　with　precise　molecular　weight　and　narrow　molecular　weight　dispersion.　Chain　extension,　monomer　compatibility　and　spatiotemporal　control　experiments　revealed　the　high　chain　end　fidelity　of　obtain　polymethacrylates　and　the　universality　of　photo-RCMP　process　by　using　synthetic　CMPs　catalysts.　The　density　functional　theory　(DFT)　calculation　reveals　that　all　the　highest　unoccupied　molecular　orbital　(HOMO)　and　the　lowest　unoccupied　molecular　orbital　(LUMO)　of　three　CMPs　are　in　junction　segment　and　connecting　segment　respectively,　which　exhibits　strong　electron　distribution　asymmetry.　Moreover,　the　DFT　and　experimental　results　verified　that　the　(donor-acceptor)　D-A　structure　with　push-pull　electron　ability　and　π-conjugated　electron　channel　promote　intermolecular　charge　transfer,　which　reduce　the　Gibbs　free　energy　of　photo-induced　RCMP　to　increase　the　electron　transport　ability　and　the　polymerization　rate.　This　work　indicates　that　by　the　construction　of　D-A　structure　and　π-conjugated　electron　channel　can　effectively　enhance　the　catalytic　properties　of　CMPs-based　photocatalysts,　which　provides　a　methodology　to　design　heterogeneous　photocatalysts　for　photo-induced　RCMP.　©　2023