Angular resolved photoelectron spectra using Hei (21.2 eV) radiation have been obtained for benzenethiol (phenyl mercaptan) chemisorbed on Cu(111), as well as for the clean surface. The correlation with the gas-phase spectra suggests that the benzenethiol bonds to copper by way of sulfur-containing orbitals rather than carbon π ring orbitals. The angular dependence of the different bands formed in the photoelectron spectra indicates that the benzene ring is oriented perpendicular or near perpendicular to the surface. XPS analysis, with Al–Kα radiation, of the Cu 2p, C 1s, and S 2p orbitals confirms the stoichiometry as well as the surface coverage. The extent of surface coverage supports the argument against benzenethiol lying flat on the copper surface.