The S 1s X-ray absorption near edge structure (XANES) and X-ray photoelectron spectra (XPS) of the neutral complexes [SbL(dmit)] (L = Br or I; dmit =1,3-dithiole-2-thione-4,5-dithiolate) have been measured using tunable synchrotron radiation. The valence shell electronic excitation by ultraviolet-visible (UV-vis) spectroscopy and the infrared vibrational spectra are presented and analyzed. The UV-vis results lead to an assignment of bands at 400 nm as π(Sm) → π*(C═S), where S(m) is the thiolate sulfur. The corresponding S 1s → π*(C═S) transition was identified at 2468.3 eV. Ab initio calculations, within the improved virtual orbital (IVO) method, carried out with the GSCF3 program, were applied to establish a complete and accurate spectral assignment. It has been the first attempt to apply such methodology for dmit coordination compounds, and very consistent results were obtained.