The possibility of the formation of PbTiO3 from a multilayer structure of PbO and TiO2 layers on Pt-coated Si substrates prepared by rapid thermal metal organic chemical vapor deposition (RTMOCVD) followed by an appropriate annealing process was examined. The metal organic precursors of PbO and TiO2 were Pb(C2H5)4 and Ti(Oi-C3H7)4, respectively. The composition of the PbTiO3 thin film was adjusted by control of the thickness of each binary oxide layer of PbO and TiO2. The multilayer structure was converted into crystalline PbTiO3 by rapid thermal annealing under O2 ambient at temperature greater than 550 ℃. As the annealing temperature was increased from 550 to 750 ℃, the peaks related to perovskite PbTiO3 in the XRD patterns became stronger and sharper. From this study, it was confirmed that the crystalline PbTiO3 thin films could be prepared from the interdiffusion reaction of multilayer structure composed of primitive binary oxides through the appropriate post annealing process.