We have performed gold deposition on Al2O3 films prepared in ultra high vacuum conditions on silicon substrates. The experiments have been followed using elastic peak electron spectroscopy (EPES) method combined with Monte-Carlo simulation of electron trajectories inside the samples. Due to its extremely high surface sensitivity, especially at 200 eV, difference in gold overlayer formation was shown for two kind of experiments: gold on alumina surface (Au/Al2O3/Si) and gold on alumina enriched with aluminium (Au/Al-0/Al2O3/Si). The presence of alumina inside the gold deposits has been detected but in different quantities. In the case of gold deposition on Au/Al-0/Al2O3/Si, we observed the oxidation of aluminium at the beginning of the process. (C) 2003 Elsevier Science B.V. All rights reserved.