A detailed analysis using X-ray photoelectron spectroscopy (XPS) is presented for the system of 2-mercapto-1-methylimidazole (MMeI) adsorbed on Cu in 3 wt% NaCl solution. High-resolution and survey XPS spectra and XPS-excited Auger L3M4,5M4,5 spectra were analysed in detail. Surface analysis revealed that the MMel molecules do not lie flat on the surface via pi-d interactions, but adsorb on the surface through an N-S-bridge configuration. Moreover, the characteristic Cu(I)-MMeI connection fingerprint, which is usually observed for these kinds of molecules, was not observed. Tougaard thickness analysis showed that a relatively thin MMel surface layer (0.3-0.6 nm) is formed on the Cu substrate after 1 h of immersion. Herein, MMeI is considered as a Cu corrosion inhibitor for chloride solution for short-term immersion periods. Based on the XPS analysis, an explanation of why MMel is not effective for longer-term immersion periods, compared with similar compounds, is given. (C) 2017 Elsevier B.V. All rights reserved.