Al-free and Al-doped V2O5 nanostructures were synthesized by a thermal-chemical vapor deposition (CVD) process on Si(100) at 850 degrees C under 1.2 x 10(-1) Torr via a vapor-solid (V-S) mechanism. X-ray diffraction (XRD), Raman, and high-resolution transmission electron microscopy (HRTEM) confirmed a typical orthorhombic V2O5 with the growth direction along [110]-direction of both nanostructures. Metallic Al, rather than Al3+-ion, was detected by X-ray photoelectron spectroscopy (XPS), affected the V2O5 crystallinity. The photoluminescence intensity of V2O5 nanostructure at 1.77 and 1.94 eV decreased with the increasing Al-dopant by about 61.6% and 59.9%, attributing to the metallic Al intercalated between the V2O5-layers and/or filled in the oxygen vacancies, which behaved as electron sinks. Thus the Al-doped V2O5 nanostructure shows the potential applications in smart windows and the electrodic material in a Li-ion battery.