GaN nanowires and nanorods have been successfully synthesized on Si (111) substrates by magnetron sputtering through ammoniating Ga2O3/Nb thin films and the effects of ammoniation temperatures on growth of GaN nanowires and nanorods were analyzed in detail. X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, high-resolution transmission electron microscopy, and photoluminescence spectra were carried out to characterize microstructures, morphologies, and optical properties of GaN samples. The results demonstrate that sample after ammoniation at 950 °C is single crystal GaN with hexagonal wurtzite structure and high crystalline quality, having the size of 30 - 80 nm in diameter. After ammoniation at 1000 °C, GaN nanorods appear with smooth and clean surface and more than 100 nm in diameter. The optical properties of GaN nanowires grown at 950 °C and nanorods grown at 1000 °C are best with strong emission intensities.