This study demonstrates, for the first time, the formation of a hemiester of carbonic acid on self-assembled monolayers using voltammetric techniques and redox probes. A gold electrode (GE) was modified with 2-mercaptoethanol (ME) through self-assembly. With this modified electrode (GE-ME), a well-defined peak was observed by differential pulse voltammetry (DPV) for the negatively charged redox probe, ferricyanide/ferrocyanide, [Fe(CN)6]3-/4-, in sodium acetate as electrolyte adjusted to pH 8.2. In the presence of dissolved CO2, there is a decrease of the ferrocyanide peak current with time (~30% in 60 min), attributed to the formation of the hemiester 2-mercapto ethyl carbonate at the GE-ME/solution interface. Similarly, dissolved CO2 also affects the electrochemical impedance measurements by increasing the resistance to the charge transfer process with time (elevation of Rct values), compatible with the formation of the hemiester. The addition of barium salt led to the displacement of the equilibrium towards BaCO3 precipitation and consequent dissociation of the hemiester, attested by the recovery of the initial ferricyanide DPV signal. With the positively charged redox probe [Ru(NH3)6]2+ no decrease in the DPV peak was observed during the formation of the hemiester by reaction with bicarbonate. The repulsion of [Fe(CN)6]3-, but not of [Ru(NH3)6]2+ suggests that the formed species is the negatively charged 2-mercapto-ethyl carbonate, i.e., the hemiester with a dissociated proton. Due to the lack voltammetric signal from the hemiester itself, the formation of a self-assembled layer of thio-alcohol followed by the gradual formation of the corresponding carbonic acid hemiester allowed to reach an elegant way to demonstrate the electrochemical formation of these species.