Covalent　organic　frameworks　(COFs)　are　ideal　heterogeneous　photocatalytic　platforms　offering　fascinating　spaces　for　manipulation　given　their　clearly　defined　structures　along　with　pre-customizable　skeletons.　Herein,　an　imine-based　COF　Im-oMe　featuring　N　and　O　sites　allowing　the　integration　of　CuII　ions　via　coordination　bonds　in　local　regions　of　the　skeleton　is　reported　for　aerobic　photoinduced　electron/energy　transfer　atom　transfer　radical　polymerization　(PET-ATRP)　in　the　aqueous　phase.　CuII@Im-oMe　of　anchored　CuII　ions　is　capable　of　triggering　skeleton　localized　polarization　effects,　producing　greater　dipole　moment　driving　force　and　facilitating　the　charge　separation　and　transport　to　enhance　its　photopolymerization　performance.　Meanwhile,　the　system　does　not　require　additional　addition　of　transition　metal　halides,　and　remains　highly　active　after　3　cycles.　The　present　work　expands　the　feasible　design　methods　and　strategies　of　heterogeneous　photocatalysts　available　for　precision　production　of　polymers　in　open-air　environments.　©　2024　Elsevier　Inc.