AbstractThe surface‐enhanced Raman scattering of benzenethiol was investigated in a silver sol. It was found that benzenethiol was chemisorbed dissociatively on the silver surface by rupture of its SH bond and the benzenethiolate formed on adsorption was bound to silver via its sulphur atom. Using the electromagnetic surface selection rule, the orientation of the benzene ring with respect to the surface plane could not be determined conclusively. However, it seemed likely that benzenethiol was adsorbed face‐on to the silver su