A strong and rather unexpected effect of stereoisomerism was observed during the electro-oxidation of the 2,3-butanediol stereoisomers. This first original observation appears to be dependent on the absolute configuration of the reactive species and on the superficial structure of the electrode surface. The activity of the electrode towards the oxidation of 2,3-butanediol stereoisomers was also found to be greatly affected by the nature of the anion of the supporting electrolyte. Electrolysis of each stereoisomer leads very selectively to the corresponding acetoine, whereas only traces of diacetyl and CO, are detected.