A simple laser ablation method has been employed for the synthesis of β-Ga2O3 nanowires. The as-synthesized products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and room-temperature photoluminescence. The synthesized β-Ga2O3 nanowires have diameters of 15−50 nm and lengths up to several micrometers, and a few of the nanowires appear to have ring-shaped structures. Photoluminescence of the bulk β-Ga2O3 nanowires shows a stable and broad green emission band centered at 497 nm, which has a blueshift of 30 nm from β-Ga2O3 powder. Possible growth mechanisms of the β-Ga2O3 nanowires are briefly discussed.