Single-crystal thin films ofPb(ZrxTi1−x)O3(PZT) covering the full compositional range (0⩽x⩽1) were deposited by metal-organic chemical vapor deposition. Epitaxial SrRuO3(001) thin films grown on SrTiO3(001) substrates by rf-magnetron sputter deposition served as template electrode layers to promote the epitaxial growth of PZT. X-ray diffraction, energy-dispersive x-ray spectroscopy, atomic force microscopy, transmission electron microscopy, and optical waveguiding were used to characterize the crystalline structure, composition, surface morphology, microstructure, refractive index, and film thickness of the deposited films. The PZT films were single crystalline for all compositions exhibiting cube-on-cube growth epitaxy with the substrate and showed very high degrees of crystallinity and orientation. The films exhibited typical root mean square surface roughness of ∼1.0–2.5 nm. For tetragonal films, the surface morphology was dominated by grain tilting resulting from ferroelectric domain formation. We report the systematic compositional variation of the optical, dielectric, polarization, and electronic transport properties of these single-crystalline PZT thin films. We show that the solid-solution phase diagram of the PZT system for thin films differs from the bulk due to epitaxy-induced strains and interfacial defect formation. High values of remanant polarization (30–55 &mgr;C/cm2) were observed for ferroelectric compositions in the range of 0.8⩽x⩽0.2. Unlike previous studies, the dielectric constant exhibited a clear dependence on composition with values ranging from 225 to 650. The coercive fields decreased with increasing Zr concentration to a minimum of 20 kV/cm forx=0.8. The undoped films exhibited both high resistivity and dielectric-breakdown strength (1013–1014&OHgr; cm at 100 kV/cm and 300–700 kV/cm, respectively). ©1997 American Institute of Physics.