Exotic oxidation states of the first-row transition metals have recently attracted much interest. In order to investigate the oxidation states of a series of iron–oxalate complexes, an aqueous solution of iron(III) nitrate and oxalic acid was studied by infrared free liquid matrix-assisted laser desorption/ionization as well as ionspray mass spectrometry. Here, we show that iron is not only detected in its common oxidation states +II and +III, but also in its unusual oxidation state +I, detectable in both positive-ion and in negative-ion modes, respectively. Vibrational spectra of the gas phase anionic iron oxalate complexes [Fe^III(C₂O₄)₂]⁻, [Fe^II(C₂O₄)CO₂]⁻, and [Fe^I(C₂O₄)]⁻ were measured by means of infrared photodissociation spectroscopy and their structures were assigned by comparison to anharmonic vibrational spectra based on second-order perturbation theory.