We　demonstrate　an　electrostatic　confinement-induced　charge　transfer　pathway　in　a　supramolecular　photocatalyst　comprising　of　an　ionic　covalent　organic　framework　(COF)　and　cationic　metal　complexes.　The　dynamic　electrostatic　interactions　not　only　attract　cations　around　the　COF　to　accept　photogenerated　electrons,　but　also　allow　for　a　retention　of　homogeneous　catalytic　characters　of　complexes,　making　a　subtle　balance.　Accordingly,　the　electrostatic　confinement　effect　facilitates　the　forward　electron　transfer　from　a　photoexcited　COF　to　cationic　Co　complex,　realizing　a　remarkable　photocatalytic　CO2　reduction　performance.　Its　catalytic　efficiency　is　far　superior　to　the　supramolecular　counterparts　with　Van-der-Waals　or　hydrogen　bonding　interactions.　This　work　presents　an　insight　for　enhancing　charge　transfer　in　supramolecular　systems,　and　provides　an　effective　approach　for　construction　of　highly　efficient　photocatalysts.　©　2024　Wiley-VCH　GmbH.