The decomposition of titanium diisopropoxide dipivaloylmethanato [: , ], a Ti precursor used in metallorganic chemical vapor deposition or in atomic layer deposition processes for producing Ti-containing films, was studied in a high vacuum chamber, maintained at a pressure of , using temperature-programmed desorption (TPD). The species present on the substrate surface at different temperatures in the TPD experiments were monitored by X-ray photoelectron spectroscopy (XPS). The isopropoxy ligand is dissociated from the Ti precursor, producing acetone and isopropanol by disproportionation at and only acetone at temperatures higher than . The dissociation of the isopropoxy ligand is complete at . The dpm ligand is dissociated to give propylene and propanal at all temperatures above and the dissociation is complete at about . The XPS results indicate that titanium oxide is formed on the substrate surface at temperatures above . The other surface component is carbon, which largely originates from the t-butyl group. The formation of titanium oxide was confirmed by a separate film-deposition experiment at relatively high pressures, , using the same Ti precursor. That is, a film deposited on Pt at high pressures showed an XPS peak for the Ti state, representing titanium oxide, as the major peak when the Ti precursor was decomposed at temperatures higher than , the temperature range for dissociation of the dpm ligand.