We have investigated the (CH3)2S/Cu(100) system using polarization dependent S K-edge near edge x-ray absorption fine structure (NEXAFS) and x-ray photoelectron spectroscopy (XPS) for both S 1s and C 1s electrons. From the XPS results, the (CH3)2S molecule is found to adsorb through the sulfur atom on the Cu(100) surface. There is a little polarization dependence in the S K-edge NEXAFS spectra for submonolayer phase. The orientation angle of the molecular plane is estimated to be 33° from the surface. © 2002 American Vacuum Society.