Epitaxial SrRuO3 thin films were deposited by RF sputtering on SrTiO3 or MgO substrates for use as underlying electrodes. On these conductive substrates, epitaxial Pb(Zr0.35Ti0.65)O3 (PZT) and PbTiO3 (PT) thin films were deposited by metalorganic chemical vapor deposition (MOCVD). X-ray diffraction (XRD), RBS channeling (RBS), transmission electron microscopy (TEM) and optical waveguiding were used to characterize the phase, microstructure, defect structure, refractive index, and film thickness of the deposited films. The PZT and PT films were epitaxial and c-axis oriented. 90° domains, interfacial misfit dislocations and threading dislocations were the primary structural defects, and the films showed a 70% RBS channelling reduction. Hysteresis and dielectric measurements of epitaxial PZT ferroelectric capacitor structures formed using evaporated Ag or ITO glass top electrode showed: a remanent polarization of 46.2 μC/cm2 a coercive field of 54.9 kV/cm, a dielectric constant of 410, a bipolar resistivity of ∼5.8×109 ω-cm at a field of 275 kV/cm, and a breakdown strength of >400 kV/cm.