A porous vanadium pentoxide (V2O5) nanomaterial was prepared by using the electrospun PMMA fibers as a template, which could be removed by annealing at high temperature leaving tube-like pores with 1μm in diameter. It is composed of numerous rice-like nanoparticles in 50–100nm size. In the potential range of 4.0–2.0V (vs. Li/Li+), it can deliver a high reversible capacity of 283mAhg−1 at 0.2C rate and exhibits an excellent rate capability (104mAhg−1 at 12C rate). Even cycled at the 4C rate, the discharge capacity still remains 85% of the initial one over 300 cycles, showing an excellent cycling performance. The results suggest the obtained V2O5 nanomaterial could develop into a promising cathode material for rechargeable lithium batteries.