Irradiation of the absorption band of an NAD (nicotinamide adenine dinucleotide) dimer analogue, 1-benzyl-1,4-dihydronicotinamide dimer, (BNA)(2), in acetonitrile containing a cyclopentadienyliron dicarbonyl dimer, [CpFe(CO)(2)](-), results in generation of 2 equiv of the cyclopentadienyliron dicarbonyl anion, [CpFe(CO)(2)](-), accompanied by the oxidation of (BNA)(2) to yield 2 equiv of BNA(+). The studies on the quantum yields, the electrochemistry, and the transient absorption spectra have revealed that the photochemical generation of [CpFe(CO)(2)](-) by (BNA)(2) proceeds via photoinduced electron transfer from the triplet excited state of (BNA)(2) to CCpFe(CO)(2)](2).