Synthesis of amorphous SiCO nanowires was carried out by means of direct current arc discharge. Free-standing SiCO nanowires were deposited on the surface of a graphite crucible without any catalyst and template. The SiCO nanowires were analyzed by XRD, SEM, TEM, XPS, and FTIR. The SiCO nanowires were typically 20–100 μm in length and 10–100 nm in diameter as measured by SEM and TEM. The XPS and FTIR spectroscopy analysis confirmed that the Si atoms share bonds with O and C atoms in mixed SiCO units. The PL spectrum of the SiCO nanowires showed strong and stable white emissions at 454 and 540 nm. A plasma-assisted vapor-solid growth mechanism is proposed to be responsible for the formation of the SiCO nanowires.