<p>Metal-coordinated covalent organic frameworks have attracted extensive attention in the field of CO₂ photoreduction to CO due to their high electron affinity and tunable structure. However, achieving efficient CO₂ activation requires overcoming the challenges of multi-electron transfer and intermediate stabilization, necessitating multifactorial optimization such as metal site cooperation, photosensitizer anchoring, and spatial alignment. Herein, we designed and fabricated a hydroxyl-functionalized COF featuring dinuclear Co/Zn sites and incorporated [Ru(phen)₃](PF₆)₂ as the photosensitizer for photocatalytic reduction of CO₂ to CO. When the ratio of Co(II) and Zn(II) in the dinuclear COF was 1:2, the obtained isostructural COF-Co₁Zn₂ showed enhanced CO production, with the CO conversion rate reached 46062 µmol g<Stack> _Co ⁻¹ </Stack> h⁻¹, which was three times higher than the CO production of the single metal COF (COF-Co: 15309 µmol g<Stack> _Co ⁻¹ </Stack> h⁻¹). DFT calculation and photoelectrochemical results supported the enhanced photocatalytic CO₂ reduction performance of COF-Co₁Zn₂. This work shows that multi-site synergistic catalysis is an effective way to optimize the catalytic performance of COF catalysts for photochemical CO₂ reduction.</p>