Optimized photocatalytic conversion of CO₂ requires new potent catalysts that can absorb visible light. The photocatalytic reduction of CO₂ using rhenium(I) has been demonstrated but suffers from low turnover. Herein, we describe a [Re(CO)₃(1-(1,10)phenanthroline-5-(4-nitro-naphthalimide))Cl] photocatalyst, which when combined with the sacrificial donor 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole, results in selective production of formic acid and a high turnover number of 533 and turnover frequency of 356 h⁻¹. Single-crystal X-ray diffraction and DFT studies are also discussed.