We have used cyanide-modified Pt(111) electrodes to investigate the size and geometry of the minimum atomic ensemble necessary for the oxidation of methanol on Pt electrodes. Poison formation on cyanide-modified Pt(111) is completely inhibited, the corresponding electrooxidation reaction proceeding, hence, exclusively through the reactive intermediate pathway. These results suggest that formation of adsorbed CO would require the presence of at least three contiguous Pt atoms.