Vanadium oxide nanotubes (VO x -NTs) are prepared by sol–gel method and subsequent hydrothermal treatment using dodecylamines as structure directing templates. After sintering of VO x -NTs in the mixed gas flow of nitrogen and oxygen, we successfully obtain a kind of nanospike shaped vanadium pentoxide free of organic template. The synthesized vanadium pentoxide nanospike (V2O5-NS) is composed of interconnected V2O5 nanocrystals (50–200 nm) and exhibits superior specific capacity and cycling performance (427 mA h g−1 for the first cycle and 218 mA h g−1 after 50 cycles at 50 mA g−1 current density between 1.5 and 4 V versus Li/Li+) when used as cathode materials for lithium ion batteries. Besides, V2O5-NS also possesses good rate capability. This novel method adopted in the work is facile and effective for the synthesis of nanostructured vanadium oxide.