The electro-oxidation of a series of selectively deuterated alcohols (2-propanol, 1,2-butanediol, 1,4-butanediol and 2,3-butanediol) at a polycrystalline gold electrode in alkaline solutions was studied with cyclic voltammetry. Results were evaluated with respect to the mechanism of the electro-oxidation and the conceivable mode of adsorptive interaction between the alcohol and the surface. Differences in electrochemical reactivity are explained in terms of the molecular structure of the transition state and the participation of adsorbed OH-species.