High-density GaN nanowires were successfully synthesized on Si(111) substrates through ammoniating Ga 2 O 3 /Nb films under flowing ammonia atmosphere at 950• C. The as-synthesized GaN nanowires are characterized by X-ray diffraction, selected-area-electron diffraction, Fourier transform infrared, scanning electron microscopy, and field-emission transmission electron microscopy. The results show that the synthesized nanowires are singlecrystal hexagonal wurtzite GaN with diameters ranging from 30 to 100 nm and lengths up to several microns. The photoluminescence spectra measured at room temperature only exhibit a strong and broad emission peak at 367.8 nm. Finally, the growth mechanism of GaN nanowires is discussed.