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Constructing a powerful photocatalytic system that can achieve the carbon dioxide (CO 2 ) reduction half-reaction and the water (H 2 O) oxidation half-reaction simultaneously is a very challenging but meaningful task. Herein, a porous material with a crystalline topological network, named viCOF-bpy-Re, was rationally synthesized by incorporating rhenium complexes as reductive sites and triazine ring structures as oxidative sites via robust -C=C- bond linkages. The charge-separation ability of viCOF-bpy-Re is promoted by low polarized π-bridges between rhenium complexes and triazine ring units, and the efficient charge-separation enables the photogenerated electron-hole pairs, followed by an intramolecular charge-transfer process, to form photogenerated electrons involved in CO 2 reduction and photogenerated holes that participate in H 2 O oxidation simultaneously. The viCOF-bpy-Re shows the highest catalytic photocatalytic carbon monoxide (CO) production rate (190.6 μmol g -1  h -1 with about 100 % selectivity) and oxygen (O 2 ) evolution (90.2 μmol g -1 h -1 ) among all the porous catalysts in CO 2 reduction with H 2 O as sacrificial agents. Therefore, a powerful photocatalytic system was successfully achieved, and this catalytic system exhibited excellent stability in the catalysis process for 50 hours. The structure-function relationship was confirmed by femtosecond transient absorption spectroscopy and density functional theory calculations., (© 2023 Wiley-VCH GmbH.)