The description of the monolayer formed at Au(1 1 1) by 2-mercaptobenzimidazole (MBI) under potential control has been based on electrochemical data (charge measurements) and spectroscopic information from the subtractively normalized interfacial Fourier transform infrared spectroscopy method (SNIFTIRS). From the quantitative analysis of the SNIFTIR spectra, a surface coverage Gamma/Gamma(max) was extracted for each sample potential. The evolution of the coverage with potential was in full agreement with the charge density curve. The shift of the pzc in the presence of MBI indicates that the adsorbed molecules have a nonzero component of the permanent dipole moment in the direction perpendicular to the electrode surface. Thanks to the high quality of the spectra, it was possible to determine the orientation of MBI molecules at the surface in the monolayer and submonolayer range. The angle between the C-2-axis of the molecule and the direction normal to the surface is close to 64 +/- 4 degrees and its small change (<15 degrees) with potential indicates that the orientation of the molecules is chiefly controlled by the chemical interaction between the sulphur atom and the gold surface. (C) 2005 Elsevier Ltd. All rights reserved.