GaN nanorods have successfully been synthesized on Si(111) substrates via ammoniating ZnO/Ga2O3 films at 950℃. Ga2O3 thin films and ZnO middle layers were deposited in t on Si(111) substrates by r.f. magnetron sputtering system. ZnO volatilized at 950℃ in the ammonia ambience and Ga2O3 reacted to NH3 to fabricate GaN nanorods in the later ammoniating process. The volatilization of ZnO layers played an important role in the fabrication. The structure and composition of the GaN nanorods were studied by X-ray diffraction (XRD) and Fourier transform infrared spectrophotometer (FTIR). The morphology of GaN nanorods was investigated using scanning electron microscopy (SEM) and transmission electronic microscope (TEM). The analyses of measured results revealed that GaN nanorods with hexagonal wurtzite structure were prepared by this method.