As prevalent cofactors in living organisms, iron–sulfur clusters participate in not only the electron-transfer processes but also the biosynthesis of other cofactors. Many synthetic iron–sulfur clusters have been used in model studies, aiming to mimic their biological functions and to gain mechanistic insight into the related biological systems. The smallest 2Fe–2S clusters are typically used for one-electron processes because of their limited capacity. Our group is interested in functionalizing small iron–sulfur clusters with redox-active ligands to enhance their electron storage capacity, because such functionalized clusters can potentially mediate multielectron chemical transformations. Herein we report the synthesis, structural characterization, and catalytic activity of a diferric 2Fe–2S cluster functionalized with two o-phenylenediamide ligands. The electrochemical and chemical reductions of such a cluster revealed rich redox chemistry. The functionalized diferric cluster can store up to four electrons reversibly, where the first two reduction events are ligand-based and the remainder metal-based. The diferric 2Fe–2S cluster displays catalytic activity toward silylation of dinitrogen, affording up to 88 equiv of the amine product per iron center.