Lead- and titanium-based oxide thin films were prepared by the metal-organic chemical vapor deposition technique (MOCVD) and the relationship between the film structures and the processing parameters, such as the ratio of Pb/Ti precursors in the gas phase, substrate materials, substrate surface orientation, and growth temperature, was systematically studied. It was found that whether a single-phase stoichiometric PbTiO3 film could be obtained depended on both the Pb/Ti precursor ratio in the gas phase and the deposition temperature. Under appropriate conditions, stoichiometric PbTiO3, films could be obtained on all the substrates including silicon, MgO, α-Al2O3, SrTiO3, and LaAlO3. The PbTiO3 films grown on silicon substrates were always polycrystalline, whereas epitaxial PbTiO3 films were obtainable on all the other substrates. For epitaxial PbTiO3 films, the epitaxial relationship, crystallinity, and domain structures were found to be a function of both the substrate materials and surface orientation as well as the deposition temperature. X-ray rocking curves (ω scan) of the (100) and (001) planes of PbTiO3 epitaxial film and PbTiO3 single crystal revealed the inherent nature of the domain structures in PbTiO3.