Growing V2O5 nanowires (NWs) on a conducting glass substrate combines gaseous transport and pyrolytic deposition of vanadium polyoxometalate anions, and yields vertically aligned vanadium-oxide nanowires. Scanning electron and transmission electron microscopy, selected-area electron diffraction, Raman spectra and powder X-ray analyses indicate that V2O5 nanowires as synthesized were single-crystalline and grew anisotropically among direction . NH2OH·HCl served not only as a reducing agent to produce vanadium polyoxometalate clusters but also as a source of NH3 gas to facilitate the vapor pyrolysis and deposition. The optical properties of V2O5 nanowires exhibit a character dependent on structure. Field emission (FE) measurements show a small turn-on field voltage ~8.3 V/μm, maximum current density 1.8 mA/cm2, and a linear Fowler-Nordheim behavior.