The electrooxidation of methanol on silver in alkaline medium has been studied by cyclic voltammetry and Fourier-transform infrared spectroscopy. It has been found that methanol electrooxidation starts together with the formation of multilayer Ag(II) oxide, which acts as a catalyst for the Former process. The only oxidation product of methanol was formate, according to in situ FTIR spectroscopy results. In a negative potential sweep after a positive potential excursion in which methanol electrooxidation took place, a small anodic peak in the potential region of the beginning of the electroreduction of the Ag underpotential oxides showed that freshly reduced Ag has some activity for the electrooxidation of adsorbed methanol residues. (C) 2000 Elsevier Science B.V. All rights reserved.