The electrochemical oxidation of methanol and related small molecules has been of special interest in relation to fuel cell research. With improvements in the design of fuel cells that operate on methanol and hydrogen gas, there has been a great deal of interest in the chemical steps involved in the oxidation of methanol and its by-products on metal electrodes. In recent years, we have approached the study of methanol oxidation pathways with the use of electrochemical and spectroscopic analysis techniques. Dissociative chemisorption leading to adsorbed carbon monoxide (CO) is probed with surface infrared spectroscopy, formaldehyde is quantified with fluorescence spectroscopy, and the conversion of adsorbed CO to carbon dioxide is investigated with linear sweep voltammetry and potential step techniques. This presentation will describe studies of methanol electrochemistry on Pt and Pt-Ru alloy solid electrodes and supported nanometer-scale catalysts. In situ infrared measurements between ambient and 85 @super o@C demonstrate methanol dissociative chemisorption is thermally activated on high Ru content bulk alloys. On solid Pt and Pt-Ru electrodes, formaldehyde can be an important by-product of methanol oxidation. However, under similar conditions the oxidation of methanol on nanometer-scale catalysts of Pt and Pt-Ru appears to be more complete. Attempts to correlate the properties of nanometer-scale metal particles and methanol oxidation pathways will be discussed.