1,6-hexanedithiol (HDT) and 1-hexanethiol (HT) molecules were bound to the surface of polycrystalline Au by using the self-assembled monolayers method. Characterizations of Au-HDT and Au-HT (Au-HTs) electrodes were performed electrochemically by the cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) methods. Blocking properties of Au HTs surfaces were examined in the Fe(CN)(6)(3-) solution by the CV. Furthermore, the isolation effect of Au-HTs electrodes on the oxidation of gold in the H2SO4 medium and desorption of HTs monolayers on the surface by being reduced in NaOH medium were examined. Additionally, characterization of Au HTs electrodes was performed by using X-ray photoelectron spectroscopy (XPS), contact angle measurement (CAM) and scanning electron microscopy (SEM) methods.