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Atomically precise Au nanoclusters (NCs) with discrete energy levels can be used as photosensitizers for CO₂ reduction. However, tight ligand capping of Au NCs hinders CO₂ adsorption on its active sites. Here, a new hybrid material is obtained by anchoring of thiol functionalized terpyridine metal complexes (metal=Ru, Ni, Fe, Co) on Au NCs by ligand exchange reactions (LERs). The anchoring of Ru and Ni complexes on Au₂₅ NC (Au₂₅−Ru and Au₂₅−Ni) leads to adequate CO₂ to CO conversion for photocoupled electrocatalytic CO₂ reduction (PECR) in terms of high selectivity, with Faradaic efficiency of CO (FE_CO) exceeding 90 % in a wide potential range, remarkable activity (CO production rate up to two times higher than that for pristine Au₂₅PET₁₈) and extremely large turnover frequencies (TOFs, 63012 h⁻¹ at −0.97 V for Au₂₅−Ru and 69989 h⁻¹ at −1.07 V vs. RHE for Au₂₅−Ni). Moreover, PECR …