Vertically well-aligned ZnO nanowire (NW) arrays with high density were directly synthesized on graphene/Si substrate by thermal evaporation of zinc powder without catalysts or additives. The ZnO NWs were characterized by field emission scanning electron microscopy (FE-SEM), high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), photoluminescence (PL), and Raman spectroscopy. The results showed that the obtained ZnO NWs have diameters in the range of 300-350 nm with lengths of several tens micrometers. The prepared ZnO NWs are of a single crystal, which have a hexagonal wurtzite crystal structure with c-axis (002) orientation growth perpendicular to the substrate surface. The NW arrays had a good crystal quality with excellent optical properties, indicating a sharp and strong ultraviolet emission at 380 nm, and a weak visible emission at around 516 nm.