A coordinatively unsaturated FeII complex bearing a pentadentate ligand (N,N′,N′-tris(2-pyridyl-methyl)-1,2-diaminoethane) functionalized with a cyclic disulfide group has been prepared in order to graft reactive metal entities as self-assembled monolayers (SAMs) on gold electrodes. Prior to grafting, exogenous ligand exchange has been investigated by cyclic voltammetry (CV) in solution, showing that the nature of the first coordination sphere (N5)FeII–X (X = Cl−, OTf−, MeCN, acetone) can be tuned, thanks to the control of the chemical conditions. The FeII complex has been immobilized on gold electrodes by spontaneous (passive) adsorption as well as by an electro-assisted method. The resulting SAMs were characterised by XPS and AFM analyses. CV experiments implementing these SAMs as working electrodes showed that the first coordination sphere of the grafted FeII complex can be controlled by adjusting the chemical conditions, similarly to the studies in a homogeneous solution. Finally, the supported FeII complex proved to be reactive with superoxide generated at the electrode surface by reduction of dissolved dioxygen. Under the employed conditions, leaking of the metal complex was not observed.