The desorption of 2-mercaptoethanesulfonate (MES) spontaneously adsorbed on Au(111) has been studied by using both potential-step and voltammetric experiments. From the amount of gold oxide formed during the oxidation sweep in the fingerprint region it is shown that the adsorption process induces structural changes of the gold surface. It is also shown that tot ether with the reductive desorption of MES ions a concomitant faradaic process occurs, The results suggest that this process is connected to the reduction of solvent on the structurally modified gold electrode, The reductive desorption process of MES undergone at more negative potentials is characterized by a single peak in the voltammetric response and the presence of a maximum in the chronoamperogram. It is shown that the logarithm of the maximum current, the time at which the maximum current appears, and the peak width at half height depend Linearly on potential. An experimental protocol for the desorption/readsorption of MES based on a potential-step experiment followed by cyclic voltammetry is outlined as an appropriate tool to analyze simultaneously the desorption of adsorbed and readsorbed MES. A linear dependence between the two desorption peak potentials and the surface concentration of adsorbate was observed. Changes in the environment surrounding the adsorbed moities and in the potential of zero charge of the electrode are shown to be the factors ruling this dependence.