The acid-base properties of native zinc oxide surfaces have been studied using X-ray photoelectron spectroscopy (XPS). The native layers of zinc oxide have been obtained by ageing mechanically polished pure zinc disks in a glass dryer for I month. Such a treatment lead to the formation of an unstable oxide layer and dehydroxylation has been observed during storage in vacuum. By following adsorption in ultrahigh vacuum of 1,2-diaminoethane (DAE) several types of active sites have been evidenced. Zinc cations react with the probe molecule following a Lewis acid/base interaction, while the hydroxyl and the carbonate-like species react following a Bronsted acid/base reaction. Although initial interaction via the Bronsted-like mechanisms is favoured, it has been shown that the resulting complexes are not stable. Under vacuum conditions, the adsorbed DAE molecules either partly desorb or modify their interaction mode with the surface to form additional Lewis-like bonded stable complexes. In addition, a cleaning effect of the molecule has been observed which lead to partial removal of the carbonate-like contamination. (C) 2007 Elsevier B.V All rights reserved.