A genuine GaAs surface is covered with a layer (similar to few nm) of native oxide pinning the surface Fermi level within the band gap of semiconductor. In this work is presented a study of GaAs surface passivation by sulfur compounds inorganic and organic (alkane thiols), a method that combines both chemical and electronic passivation. At the surface of GaAs it is developed an adherent layer of sulfur compound as a result of chemical interaction of sulfur ions with GaAs surface, a compound putted into evidence by scanning electron microscopy (SEM) images, photoluminescence analysis, second harmonic generation (SHG) measurement and Raman spectroscopy. Using X-ray photoelectron spectroscopy (XPS) it is putted into evidence the presence of covalent bonds Ga-S and AsS as a result of chemical interaction with sulf ions. Electrical characteristic of AuGeNi/thiol/GaAs structure is presented in I (V) recorded in the region of small currents.