Flower-shape clustering GaN nanorods are successfully synthesized on Si(lll) substrates through ammoniating Ga2O3/ZnO films at 950°C. The as-grown products are characterized by x-ray diffraction (XRD), scanning electron microscope (SEM), field-emission transmission electron microscope (FETEM), Fourier transform infrared spectrum (FTIR) and fluorescence spectrophotometer. The SEM images demonstrate that the products consist of flower-shape clustering GaN nanorods. The XRD indicates that the reflections of the samples can be indexed to the hexagonal GaN phase and HRTEM shows that the nanorods are of pure hexagonal GaN single crystal. The photoluminescence (PL) spectrum indicates that the GaN nanorods have a good emission property. The growth mechanism is also briefly discussed.