The electrochemical reactivity of propanediol, butanediol, pentanediol, hexanediol and heptanediol, on polycrystalline platinum and gold electrodes, was studied in acid and alkaline media. The effect of the number of carbon atoms, i.e. the chain length, was observed. The apparent energies of activation were evaluated systematically and discussed in relation to the molecular structure of the different diols. In the case of the butanediol isomers, an effect of the alcohol group positions on the activation energy and reaction mechanisms was clearly shown.