Zinc oxide (ZnO) thin films have emerged as one of the most promising oxide materials owing to their optical and electrical properties, together with their high chemical and mechanical stability. Chemical solution deposition (CSD) is attractive technique for obtaining ZnO thin films and has the advantages of easy control of the film composition and easy fabrication of a larger-area thin film at low cost. In this work, epitaxial ZnO thin films on SiC substrate were prepared by using a CSD method with a zinc naphthenate precursor. Precursor films were pyrolyzed at 500°C for 10 min in air and finally annealed at 600°C, 700°C, 800°C and 900°C for 30 min in air. Crystallinity and in-plane alignment of the films were investigated by X-ray diffraction theta-2 theta scan and pole-figure analysis. Scanning electron microscope, scanning probe microscope, and He-Cd laser (325 nm) are used to detect the surface morphology and photoluminescence of the films. The effects of annealing temperature on crystallinity and epitaxy of the films will be fully discussed on the basis of the results of X-ray diffraction analysis.