Monoclinic gallium oxide (β-Ga2O3) nanowires were catalytically synthesized by electric arc discharge of GaN powders mixed with a small amount (less than 5 %) of transition metals under a pressure of 500 Torr (80 %-Ar + 20 %-O2). Scanning electron microscope (SEM) and high-resolution transmission electron microscope (HRTEM) images showed that the average diameter of the wires were about 30 nm and their lengths were as long as up to one hundred micrometer, resulting in extremely large aspect ratio. Fourier diffractogram was indicative of single crystalline nature of the β-Ga2O3 wire. HRTEM image also showed β-Ga2O3 with twin defects at the center of the wire which might play as nucleation seeds. Both X-ray diffraction (XRD) patterns and FT-Raman spectra of the wires identified the observed nanowires as monoclinic crystalline gallium oxides.