In the present study, Fe as a catalyst was used to grow single crystalline monoclinic gallium oxide (β-Ga2O3) nanowires using chemical-vapor-deposition method. The morphology, structure and luminescence properties of the as-grown β-Ga2O3 nanowires were investigated using various characterization techniques. The diameter of the as-grown nanowires was in the range of 50 to 100 nm, and the lengths up to tens of micrometers. The structural investigation of the nanowires was carried out using X-ray diffraction that showed monoclinic phase of Ga2O3. Further, the transmission electron microscope (TEM) investigations along with selected area diffraction pattern revealing single crystalline nature of the nanowires. The as-grown β-Ga2O3 nanowires had preferred orientation along [1-1-1] direction. The high resolution TEM image showed regular arrangement of atoms and the lattice spacing between (1-1-1) planes was around 0.266 nm. The luminescence properties of the as-grown nanowires were measured using cathodoluminescence (CL) spectroscopy. The CL measurements of β-Ga2O3 nanowires revealed a strong broad UV-blue emission band and a weak red emission band.