This paper reports that β-Ga2O3 nanorods have been synthesized by ammoniating Ga2O3 films on a V middle layer deposited on Si(111) substrates. The synthesized nanorods were confirmed as monoclinic Ga2O3 by x-ray diffraction,Fourier transform infrared spectra. Scanning electron microscopy and transmission electron microscopy reveal that the grownβ-Ga2O3 nanorods have a smooth and clean surface with diameters ranging from 100 nm to 200 nm and lengths typically up to 2μm. High resolution TEM and selected-area electron diffraction shows that the nanorods are pure monoclinic Ga2O3 single crystal. The photolumineacence spectrum indicates that the Ga2O3 nanorods have a good emission property. The growth mechanism is discussed briefly.