Metal-ligand cooperation is an important aspect in earth-abundant metal catalysis. Utilizing ligands as electron reservoirs to supplement the redox chemistry of the metal has resulted in many new exciting discoveries. Here, we demonstrate that iron bipyridine-diimine (BDI) complexes exhibit an extensive electron-transfer series that spans a total of five oxidation states, ranging from the trication [Fe(BDI)]³⁺ to the monoanion [Fe(BDI]^-1. Structural characterization by X-ray crystallography revealed the multifaceted redox noninnocence of the BDI ligand, while spectroscopic (e.g., ⁵⁷Fe Mössbauer and EPR spectroscopy) and computational studies were employed to elucidate the electronic structure of the isolated complexes, which are further discussed in this report.