Epitaxial PbTiO3 films were prepared by metalorganic chemical‐vapor deposition on MgO(001)‐, SrTiO3(001)‐, and LaAlO3(001)‐oriented substrates. Four‐circle x‐ray diffraction, transmission electron microscopy, Rutherford backscattering (RBS) channeling, and optical waveguiding were performed to characterize the deposited films. Epitaxial, single‐crystal films were obtained on all three substrate materials under the same growth conditions. However, the defect structure of the films, including grain tilting, threading dislocation density, and 90° domain formation, was strongly dependent on the choice of substrate material. Films grown on MgO(001) and LaAlO3(001) (pseudocubic indices) substrates are nominally c‐axis oriented; however, the PbTiO3 grains in the film form a fourfold domain structure, with the grains tilted ∼0.6° and ∼0.7°, respectively, toward the  directions (cubic or pseudo‐cubic) of the substrates. In addition, these films contain a significant volume fraction of 90°‐domain (a‐axis) structures with a critical thickness hc for domain formation below the detection level of our experiments (hc≥100 Å). Together, these structural defects result in a low RBS channeling yield reduction. In contrast, films grown on SrTiO3(001) substrates showed no tilting of the c‐axis grains and a minimum RBS channeling yield of as low as ∼3%. In addition, we observed that below a critical film thickness of hc∼1500 Å, 90° domain formation was completely suppressed resulting in a nearly perfect single‐crystal structure. The refractive indices and optical birefringence of the films were measured as a function of wavelength using the film‐prism coupling method. Both the ordinary and extr- aordinary refractive indices for films grown on MgO(001) and LaAlO3(001) were higher than that of single‐crystal PbTiO3; however, the optical birefringence of films grown on MgO(001) was reduced from that of the bulk. For films grown on SrTiO3(001), the ordinary refractive index was very close to that of single‐crystal PbTiO3. We correlate the refractive index values and the reduced birefringence to the degree of residual strain and the volume fraction of 90° domains in the samples, respectively. © 1995 American Institute of Physics.