Mesoporous V(2)O(5) nanofibers were fabricated by a method combining sol-gel processing with electrospinning followed by annealing in air. The resultant nanofibers were 350 nm in diameter and consisted of porous polycrystalline vanadium oxide with a specific surface area of similar to 97 m(2) g(-1). The mesoporous V(2)O(5) nanofibers demonstrated a significantly enhanced Li ion storage capacity of above 370 mA h g(-1) and a high charge/discharge rate of up to 800 mA g(-1) with little cyclic degradation.