Spherical porous vanadium pentoxide (V2O5) phase is synthesized by a spray-pyrolysis method followed by heat-treatment, as confirmed by powder X-ray diffraction. Under high-resolution electron microscope observation, the as-prepared particles are spherical and porous, with uniform particle size. On investigation of the electrochemical properties of V2O5 synthesized by this method, it is found that the initial specific capacity of the V2O5 is 399mAhg−1, and it exhibits good cycleability during the discharge and charge processes. The experimental results suggest that V2O5 synthesized by this method could be a promising electrode material for lithium-ion batteries.