The composition, electronic structure and molecular orientation of a self-assembled monolayer (SAM) of benzenethiolate on the Cu(1 0 0) surface have been investigated by means of X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS). An ordered benzenethiolate SAM with c(2 × 6) superstructure has been obtained by the reaction of diphenyldisulfide with the Cu(1 0 0) surface at room temperature. S 2p and C 1s XP spectra show S-Cu bond formation without significant thiolate decomposition. The strong dichroic signal of C K-edge NEXAFS upon varying polarization angle indicates upstanding of the adsorbed molecules with the benzene ring tilted by 20° from the surface normal. © 2009 Elsevier B.V. All rights reserved.