Hexamethyldisilathiane was successfully used as a new precursor for the formation of S layers on Au and to study their interaction. Characterization of the S modified gold surface was done by X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and scanning tunneling microscopy (STM). Key findings include the direct observation by STM of (i) coexistence of different phases, (ii) multiple sulfur layers formation, (ii) formation of rectangular structures not only on the adlayer but also on the top layer, and (iv) rectangular structure mobility on different layers. These results provide dear evidence regarding the adsorbate nature of the rectangular structures, solving a highly debated question.