Thin titanium dioxide films were produced by metalorganic chemical vapor deposition on sapphire(0001) in an ultrahigh vacuum (UHV) chamber. A method was developed for producing controlled submonolayer depositions from titanium isopropoxide precursor. Film thickness ranged from 0.1 to 2.7 nm. In situ X-ray photoelectron spectroscopy (XPS) was used to determine film stoichiometry with increasing thickness. The effect of isothermal annealing on desorption was evaluated. Photoelectron peak shapes and positions from the initial monolayers were analyzed for evidence of interface reaction. Deposition from titanium isopropoxide is divided into two regimes: depositions below and above the pyrolysis temperature. This temperature was determined to be 300 deg C. Controlled submonolayers of titanium oxide were produced by cycles of dosing with titanium isopropoxide vapor below and annealing above 300 deg C. Precursor adsorption below the pyrolysis temperature was observed to saturate after 15 minutes of dosing. The quantity absorbed was shown to have an upper limit of one monolayer. The stoichiometry of thin films grown by the cycling method were determined to be TiO2. Titanium dioxide film stoichiometry was unaffected by isothermal annealing at 700 deg C. Annealing produced a decrease in film thickness. This was explained as due to desorption. Desorption ceased at approximately 2.5 to 3 monolayers, suggesting bonding of the initial monolayers of film to sapphire is stronger than to itself. Evidence of sapphire reduction at the interface by the depositions was not observed. The XPS O is peak shifted with increased film thickness. The shifts were consistent with oxygen in sapphire and titanium dioxide having different O is photoelectron peak positions. Simulations showed the total shifts for thin films ranging in thickness of 0.1 to 2.7 nm to be -0.99 to -1.23 eV. Thick films were produced for comparison.