Vertical ZnO nanowires were successfully grown on epitaxial ZnO (002) buffer layer/Si (100) substrate. The nanowire growth process was controlled by surface morphology and orientation of the epitaxial ZnO buffer layer, which was deposited by radio-frequency (rf) sputtering. The copper catalyzed the vapor-liquid-solid growth of ZnO nanowires with diameter of approximately 30 nm and length of approximately 5.0 microm. The perfect wurtzite epitaxial structure (HCP structure) of the ZnO (0002) nanowires synthesized on ZnO (002) buffer layer/Si (100) substrate results in excellent optical characteristics such as strong UV emission at 380 nm with potential use in nano-optical and nano-electronic devices.