Vertically well-aligned ZnO nanowire (NW) arrays were synthesized directly on GaN/sapphire and Si substrate from Zn vapor deposition without catalysts. Experimental results showed that the number density, diameter, crystallinity and degree of the alignment of ZnO NWs depended strongly on both the substrate position and kind of the substrates used for the growth. The photoluminescence (PL) characteristics of the grown ZnO NW arrays exhibit a strong and sharp ultraviolet (UV) emission at 379 nm and a broad weak emission in the visible range, indicating that the obtained ZnO NWs have a high crystal quality with excellent optical properties. The as-grown ZnO NWs were characterized by using scanning electron microscopy (SEM), high resolution transmission electronic microscopy (HR-TEM), and X-ray diffraction (XRD).