Orientation and charge transfer upon adsorption of thioethanol on copper surface at room temperature has been studied by near edge x-ray absorption fine structure (NEXAFS) and x-ray photoelectron spectroscopy (XPS) techniques. It is found that thioethanol adsorbs dissociatively on the Cu(111) surface. Polarization dependent SK-edgeNEXAFS indicates that the S-C bond is tilted 47 +/- 7degrees from the surface. Above 400 K, the S-C bond breaks and creates atomic sulfur. An amount of charge transfer (one electron) from copper to thioethanol molecules was measured using S 1s XPS. (C) 2004 American Vacuum Society.