An x-ray photoelectron spectroscopy ͑XPS͒ analysis of Nb/Al wedge bilayers, oxidized by both plasma and natural oxidation, is reported. The main goal is to show that the oxidation state-i.e., O:͑oxidize͒Al ratio-, structure and thickness of the surface oxide layer, as well as the thickness of the metallic Al leftover, as functions of the oxidation procedure, can be quantitatively evaluated from the XPS spectra. This is relevant to the detailed characterization of the insulating barriers in ͑magnetic͒ tunnel junctions.