The electrochemical oxidation of methanol and related small molecules has been of special interest in relation to fuel cell research. The development of fuel cells that operate below 100 °C on methanol, or H2 has stimulated interest in the reaction steps involved in methanol and carbon monoxide oxidation at metal electrodes. In addition to being a by-product of methanol oxidation, carbon monoxide can also be present as an impurity in H2. Adsorption of carbon monoxide on the anode catalyst generally degrades its performance. We have approached the study of methanol and carbon monoxide oxidation with the use of electrochemical techniques in combination with in situ infrared spectroscopy and wet-analytical methods. This presentation will focus on the surface electrochemistry of methanol and carbon monoxide at nanometer scale Pt and bimetallic Pt materials. Catalysts are adsorbed onto smooth gold and highly ordered pyrolytic graphite (HOPG) electrodes. Gold enables infrared sampling in a standard reflectance geometry, while HOPG allows particle characterization with respect to size distribution and spatial arrangement by atomic force microscopy. Properties of nanometer-scale metal particles in relation to CO oxidation and methanol oxidation pathways will be discussed.