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The photocatalytic reduction of CO2 into fuels offers the prospect for creating a new CO2 economy. Harnessing visible light‐driven CO2‐to‐CO reduction mediated by the long‐lived triplet excited state of rhenium(I) tricarbonyl complexes is a challenging approach. We here develop a series of new mononuclear rhenium(I) tricarbonyl complexes (Re‐1−Re‐4) based on the imidazole‐pyridine skeleton for photo‐driven...