Amorphous V 2 O 5 films were prepared on glass substrates at room temperature by magnetron sputtering and converted to β-V 2 O 5 nanorods by subsequent annealing in O 2 flux. X-ray absorption near-edge spectroscopy and photoelectron spectroscopy with synchrotron radiation have been applied to confirm whether the nanorods are V 2 O 5 compound, and to investigate their electronic structure. The optical properties of the V 2 O 5 nanorods were also characterized by UV–Vis spectroscopy. It was observed that the absorption edge had an obvious red shift. The growth mechanism of the nanorods and the relationship between the microstructure and the optical properties are briefly discussed.