Epitaxial lead zirconium titanate (PZT) (001) thin films with a Pt bottom electrode were deposited by rf sputtering onto Si(001) single crystal substrates with a Ag buffer layer. Both PZT(20/80) and PZT(53/47) samples were shown to consist of a single perovskite phase and to have the (001) orientation. The orientation relationship was determined to be PZT(001)||Pt(001)||Ag(001)||Si(001). The microstructure of the multilayer was studied using transmission electron microscopy (TEM). The electron diffraction pattern confirmed the epitaxial relationship between each layer. The measured remanent polarization Pr and coercive field Ec of the PZT(20/80) thin film were 26 μC/cm2 and 110 kV/cm, respectively. For PZT(53/47), Pr was 10 μC/cm2 and Ec was 80 kV/cm.