In contrast to the UV-photoinduced ligand photoionization of the flavonoid complexes of Fe III , redox reactions initiated in ligand-to-metal charge-transfer excited states were observed on irradiation of the quercetin (1) and rutin (2) were flash-irradiated at 351 nm. Transient spectra observed in these experiments showed the formation of radical ligands corresponding to the one-electron oxidation of L and the reduction of Cu II to Cu I . The radical ligands remained coordinated to the Cu I centers, and the substitution reactions replacing them by solvent occurred with lifetimes t < 350 ns. These are lifetimes shorter than the known lifetimes (t > 1 ms) of the quercetin and rutin radicals decay.