Epitaxial Pb(Zr,Ti)O3 (PZT) thick films of 2.0–3.0 μm thickness were grown at 600 °C on (100)cSrRuO3||(100)SrTiO3 and (100)cSrRuO3||(100)LaNiO3||(100)CaF2 substrates by pulsed-metal organic chemical vapor deposition. All films showed (100) and/or (001) orientations with tetragonal symmetry. It was found that there is an almost linear relationship between the estimated thermal strain from the deposition temperature to the Curie temperature and the volume fraction of (001) orientation in the mixture of (100) and (001) orientations for the films on both substrates. Consequently, the perfectly (001)-oriented, i.e., polar-axis-oriented, PZT thick films were obtained on CaF2 with the Zr/(Zr+Ti) ratio from 0.20 to 0.40. Moreover, the lattice parameter of a- and c-axes and their ratio (c/a) of those polar-axis-oriented films were almost the same as the reported data for the powder, suggesting that the large strain is not remaining in those films. The relative dielectric constant (εr) of the polar-axis-oriented Pb(Zr0.35Ti0.65)O3 thick film on CaF2 was 180 at 1 kHz, which is lower than that of (100)/(001)-oriented thick films on SrTiO3 but almost agrees with the theoretically cal- culated value for the c-axis of PZT single crystals. Well saturated polarization-electric-field hysteresis loops with a good square shape were observed for the polar-axis-oriented thick films, and the saturation polarization and the coercive field values were 74 μC/cm2 and 64 kV/cm, respectively. These data clearly show that the electrical properties of the polar-axis-oriented epitaxial thick films are similar to the theoretical predictions for PZT single crystals.