The iron(ii) complex bearing the 2,2':6',2'':6'',2''':6''',2''''-quinquepyridine (qnpy) ligand, [Fe(qnpy)(H2O)2]2+, is a highly efficient and robust catalyst for photocatalytic reduction of CO2 to CO in aqueous acetonitrile solution. A turnover number (TON) for CO of up to 14 095 with 98% selectivity can be achieved using Ru(phen)3Cl2 (phen = 1,10-phenanthroline) as the photosensitizer and BIH (1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole) as the sacrificial reductant in a CO2-saturated MeCN/H2O (1 : 1, v/v) solution under visible light irradiation. This Fe complex is state-of-the-art for CO2 visible-light-driven catalysis.