Abstract:　Covalent　organic　frameworks　(COFs)　are　emerging　as　a　class　of　photocatalyst　for　solar　energy　utilization.　The　separation　of　photogenerated　excitons　in　COFs　is　crucial　for　their　photocatalytic　performance.　Herein,　we　report　a　strategy　to　tune　the　electronic　structure　of　COFs　by　implanting　Zn　ions　within　the　framework　to　facilitate　the　separation　and　utilization　of　the　photoinduced　charges.　Zn　ions　are　incorporated　within　the　shell　of　hollow　COF　cages　(Zn@H-TpPa)　by　a　sacrificial　template　method　with　a　formation　of　hollow　cages.　The　implantation　of　Zn　ions　within　the　framework　results　in　a　redistribution　of　electron　density　and　an　increment　of　the　polarity　of　the　COF,　as　evidenced　by　experimental　and　computational　analyses,　and　thus　contributes　to　the　separation　and　transport　of　charge　carries.　The　Zn@H-TpPa　shows　enhanced　photocatalytic　H2　production　efficiency　as　compared　to　TpPa.　The　results　demonstrate　a　new　way　to　optimize　the　electronic　structure　of　COFs　for　photocatalysis.　©　2022　Wiley-VCH　GmbH