An electrochemical and spectroelectrochemical study of the adsorption and oxidation of methanol on platinum single-crystal electrodes was carried out in alkaline media (Na2CO3 and NaOH). The adsorbed species were identified by Fourier transform IR (FTIR) spectroscopy as linearly and multibonded CO in a ratio which depends on the orientation of the electrode surface. From the FTIR spectra obtained during the oxidation of methanol, formate and CO2 have been identified as the main soluble reaction products in alkaline solution.