The formation and reductive desorption of self-assembled monolayers of 6-mercaptohexanol on mercury has been studied by using cathodic stripping voltammetry and capacitative transients, including the possibility of expanding or contracting the electrode area at the end of the preconcentration step. Experimental evidence shows the existence of three sequential stages during the formation of a thiol self-assembled monolayer. Each of these stages can be associated to the presence of (i) a low surface density state of oxidized thiol molecules, characterized by a single electrodimerization wave, (ii) a high surface density state, characterized by the emergence of a second voltammetric wave, and (iii) an ordered monolayer, which gives rise to a voltammetric spike. On the basis of electrode expansion experiments, a method is described to determine the surface concentrations of oxidized products, which does not require a baseline subtraction of the voltammograms to account for the nonfaradaic current. Quantitative voltammetric fits are consistent with the initial formation of a mixture of noninteracting monomers and dimers of oxidized thiol. The value of the maximum surface concentration and the ability to block the RU(NH3)(6)(3+) electron transfer reveal that oxidized thiol molecules adopt a nearly perpendicular orientation in the high surface density state, which hampers ionic permeation. A theoretical model is proposed to account for the observed voltammetric behavior. The transition from the lower to the higher surface density states is modeled as a chemical step involving the exchange of metal free sites. Capacitative transients are also interpreted in terms of the three-stages model.