The electrocatalytic oxidation of the different stereoisomers of 2,3-butanediol was studied at platinum single crystal electrodes with a well-defined surface. It was clearly demonstrated that the absolute configuration plays a key role in the adsorption and electrooxidation of these compounds. An important structural effect of the electrode surface was also seen. The main point observed was the strong poisoning encountered during the oxidation of the (S,S) isomer whatever the crystallographic orientation. Conversely, the meso isomer was oxidized without visible poison formation, particularly on the Pt(111) face. A complete interpretation of these phenomena is difficult. However, the important differences observed during the adsorption step can be related to the ease of formation of hydrogen bonding between the two alcohol groups of the diol.