Metal-organic chemical vapor deposition of TiO2 via pyrolysis using Ti (OC3H7)4 and N2O was investigated with the goal of producing TiO2 epitaxial films on p-Si(100) substrates. X-ray diffraction analysis showed that the grown TiO2 layer was a polycrystalline film. Auger depth profiles demonstrated that the TiO2/Si interface was relatively abrupt, and transmission electron microscopy verified the formation of an interfacial layer in the TiO2/Si interface and the formation of a polycrystalline TiO2 thin film. These results indicate that the failure to form the TiO2 epitaxial films originated from the formation of an interfacial amorphous layer at the initial growth stage.