V2O5 micro/nanorods are produced through the heat treatment for the electrospun composite fibers which are prepared by using inexpensive NH4VO3 and H2C2O4 as starting materials at room temperature. Powder X-ray diffraction analysis reveals that the micro/nanorods are orthorhombic V2O5 (space group Pmmn (59), a =1.1516, b =0.3566, c =0.4373nm), and the results of field emission scanning electron microscopy indicate that the V2O5 micro/nanorods have a diameter of roughly 300nm and a length-to-diameter ratio of 5–10. Meanwhile, the V2O5 micro/nanorod cathodes show a high lithium storage performance with the first discharge capacity of 418.8mAhg−1 and the 50th discharge capacity of 180.5mAh g−1 when the half cell is cycled between 2.0 and 4.0V at a current density of 50mAg−1. This is possibly attributed to the fact that the micro/nanostructure samples are well dispersive and they have high structural stability and efficient electron/ion transport in the charging and discharging processes.