Here we present our recent work on the fabrication of high crystalline and optical quality ZnO films on sapphire (001) by pulsed laser deposition. The influence of deposition parameters such as the substrate temperature, oxygen pressure, laser fluence, and pulse repetition rate on the crystalline quality of ZnO layers has been studied. The Ω-rocking curve FWHM of the (002) peak for the films grown at 750°, oxygen pressure 10−5 Torr was 0.17°. The XRD-Ф scans studies revealed that the films were epitaxial with a 30° rotation of the unit cell with respect to the sapphire to achieve a low energy configuration for epitaxial growth. The high degree of crystallinity was confirmed by ion channeling technique providing a minimum Rutherford backscattering yield of 2–3% in the near surface region (-2000Å). The atomic force microscopy revealed smooth hexagonal faceting of the films. The optical absorption edge measured by UV-Visible spectroscopy was sharp at 383 nm. Excellent crystalline properties of these epi-ZnO/sapphire heterostractures are thus promising for III-V nitride heteroepitaxy.