It is shown for the first time that it is possible to employ electrochemical in situ Fourier transform infrared (FTIR) spectroscopy to study the electro-oxidation of methanol at small platinum particles. A number of differences with respect to the behaviour at a bulk metal electrode are observed; these observations demonstrate beyond doubt the very significant difference between bulk and particle electrode mechanisms for the oxidation of methanol, and reveal the dangers of extrapolating from the former to the latter.