Chemically synthesized atomically precise gold clusters stabilized by triphenylphosphine ligands [Au 9 (PPh 3 ) 8 ](NO 3 ) 3 ] were deposited onto the surface of titania fabricated via atomic layer deposition. The titania surface was pretreated by heating and sputtering. After deposition of the clusters onto pretreated titania, the samples were heated at 200 °C for 20 min under ultrahigh vacuum and subsequently investigated using metastable-induced electron spectroscopy to study the electronic structure of the outermost layer of the sample and X-ray photoelectron spectroscopy to determine the chemical composition of the surface of the sample. The former study revealed that two reference spectra are needed to explain the electronic structure of the sample. One reference spectrum is related to the titania substrate, while the second spectrum is related to the presence of the Au cluster cores and the ligands removed from the cluster cores. The latter study found that the Au 4f peak is shifted to lower binding energy and the P 2p peak to higher binding energy after heating. These are interpreted in the light of ligand removal and size evolution of Au particles upon heating of the clusters on titania. The important outcome of the present work is that defects introduced at the ALD titania surface via sputtering and heating strongly reduce the agglomeration of the Au clusters adsorbed to the surface.