GaN nanowires were synthesized through the Ni-catalyzed chemical vapor deposition (CVD) method using Ga2O3/GaN mixtures as gallium sources, and precursor-substrate distances were investigated as the important factor for the growth of GaN nanowires. The microstructure, composition, and photoluminescence property were characterized by X-ray diffraction, field emission scanning electron microscopy, high-resolution transmission electron microscopy, and photoluminescence spectra. The results showed that single crystalline GaN nanowires with the diameter of about 90 nm and the length up to tens of micrometers had been grown thickly across Si (100) substrates with uniform density. Moreover, the variations of the GaN nanowire morphology, density, and size were largely attributed to substrate positions which would influence Ga precursor density in the carrier gas, the saturation degree of gaseous reactants, and the catalyst activity, respectively, in the fabrication of GaN nanowires by the vapour liquid solid mechanism.