Size-selected gold clusters, Au-n(+) (n = 1, 3, 4), were deposited on an ordered Al2O3 film grown on NiAl(110), and changes in morphology and electronic properties with deposition/annealing temperature and cluster size were investigated by X-ray photoelectron spectroscopy (XPS) and ion-scattering spectroscopy (ISS). Extensive agglomeration was observed by ISS for annealing temperatures above 300 K, accompanied by large shifts in the Au XPS binding energy. Agglomeration is more extensive in room-temperature deposition, compared to samples prepared by low-temperature deposition, then annealed to room temperature. Agglomeration is also observed to be dependent on deposited cluster size. CO adsorption was studied by ISS and temperature-programmed desorption, and we looked for CO oxidation under conditions where substantial activity is seen for Au-n/TiO2. No activity was observed for Au-n/Al2O3. The differences between the two systems are interpreted in terms of the nature of the metal-support interactions.