The mode of adsorption of (methylamino)ethanol on aluminum surfaces is shown by static SIMS and XPS to depend on the surface condition. Aluminum surfaces with ultrathin oxide overlayers react to give an alkoxy adsorbed species. Adsorption of (methylamino)ethanol on bulk alumina is not strong enough to retain the compound in vacuum at ambient temperature unless Bronsted acid sites are present. Phosphoric acid anodized aluminum behaves like bulk alumina with acid sites. Comparison of the adsorption behavior of amine alcohols with that of amides shows that the high basicity of the former is a major factor in their adsorption.