The surface chemistry of two corrosion inhibitors, 1-hydroxybenzotriazole (BTAOH) and benzotriazole (BTAH), adsorbed on copper from 3% NaCl aqueous solution, was investigated by X-ray photoelectron spectroscopy (XPS). Surface and subsurface chemical structure, composition, and layer thickness were obtained from angle-resolved XPS measurements, from detailed analysis of the background in the XPS spectra by the Tougaard method, and from XPS depth profiling performed by Ar-ion sputtering. The main concern was the shape of the X-ray induced Auger Cu L3M4,5M4,5 spectrum that offers the possibility to investigate the Cu(I) environment. The Auger Cu L3M4,5M4,5 spectrum obtained after treatment in the BTAH-containing solution was decomposed into three components originating from the Cu(I)BTA complex layer, the Cu2O underlayer, and the Cu substrate. This procedure indicates the formation of the Cu(I)BTA surface complex on the Cu2O underlayer after BTAH treatment. The BTAH molecules [either in the Cu(I)BTA complex or uncomplexed] are directed toward the Cu surface through their triazole N atoms. In contrast to the BTAH treatment, the Cu-BTAOH layer formed on the Cu surface after treatment in the BTAOH solution is less ordered and is much thinner than the Cu-BTAH structure.