Porous V2O5 nanotubes, hierarchical V2O5 nanofibers, and single-crystalline V2O5 nanobelts were controllably synthesized by using a simple electrospinning technique and subsequent annealing. The mechanism for the formation of these controllable structures was investigated. When tested as the cathode materials in lithium-ion batteries (LIBs), the as-formed V2O5 nanostructures exhibited a highly reversible capacity, excellent cycling performance, and good rate capacity. In particular, the porous V2O5 nanotubes provided short distances for Li+-ion diffusion and large electrode–electrolyte contact areas for high Li+-ion flux across the interface; Moreover, these nanotubes delivered a high power density of 40.2 kW kg−1 whilst the energy density remained as high as 201 W h kg−1, which, as one of the highest values measured on V2O5-based cathode materials, could bridge the performance gap between batteries and supercapacitors. Moreover, to the best of our knowledge, this is the first preparation of single-crystalline V2O5 nanobelts by using electrospinning techniques. Interestingly, the beneficial crystal orientation provided improved cycling stability for lithium intercalation. These results demonstrate that further improvement or optimization of electrochemical performance in transition-metal-oxide-based electrode materials could be realized by the design of 1D nanostructures with unique morphologies.