Ferricytochrome c has been previously shown to photoreduce in the presence of ferrocyanide anions, but the process has been poorly understood. Here, we propose a kinetic model for this phenomenon and support it with resonance Raman measurements that show a clear dependence of photoreduction on the concentration of mixture components and laser power. Our data are consistent with the photoreduction process that is driven by photoexcitation of the heme followed by an electron transfer from the excited state of the heme macrocycle to the heme iron. Concomitantly, the hole in the heme ground state is filled with an electron transferred from a ferrocyanide ion residing in the heme pocket.