The use of commercial 316L stainless steel as a simple, stable and competitive oxygen-evolution electrode in alkaline media for aqueous lithium–air batteries has been studied. In addition to the electrochemical characterization, the electrode was analyzed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray energy dispersive spectroscopy (X-EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Raman spectroscopy and elemental analyses via inductively coupled plasma atomic emission spectroscopy (ICP-AES). The spontaneous formation of a catalytic film, during the aging test, gives rise to interesting electrode performances. Indeed, this film, containing a large part of nanocrystalline nickel oxides (83 at% of cationic composition), catalyzes the oxygen evolution reaction via two phenomena: an increase of the roughness of the electrode surface and a hypo–hyper d interbonding effect, due to the presence of well dispersed additives of Fe and Cr in the film.