The adsorption and thermal decomposition of CH3OH on clean polycrystalline Al has been studied using UPS, XPS, and thermal desorption techniques in the temperature range 110–773 K. Molecular adsorption of CH3OH occurs at 110 K; heating leads to a surface intermediate at ∠150 K which persists until 525 K. Beginning at 525 K CH4, CO, CO2, and H2 are evolved and by 773 K the surface is oxidized. The nature of the surface intermediate is discussed.