Ultralong hierarchical vanadium oxide nanowires with diameter of 100-200 nm and length up to several millimeters were synthesized using the low-cost starting materials by electrospinning combined with annealing. The hierarchical nanowires were constructed from attached vanadium oxide nanorods of diameter around 50 nm and length of 100 nm. The initial and 50th discharge capacities of the ultralong hierarchical vanadium oxide nanowire cathodes are up to 390 and 201 mAh/g when the lithium ion battery cycled between 1.75 and 4.0 V. When the battery was cycled between 2.0 and 4.0 V, the initial and 50th discharge capacities of the nanowire cathodes are 275 and 187 mAh/g. Compared with self-aggregated short nanorods synthesized by hydrothermal method, the ultralong hierarchical vanadium oxide nanowires exhibit much higher capacity. This is due to the fact that self-aggregation of the unique nanorod-in-nanowire structures have been greatly reduced because of the attachment of nanorods in the ultralong nanowires, which can keep the effective contact areas of active materials, conductive additives, and electrolyte large and fully realize the advantage of nanomaterial-based cathodes. This demonstrates that ultralong hierarchical vanadium oxide nanowire is one of the most favorable nanostructures as cathodes for improving cycling performance of lithium ion batteries.