Porous nanostructured vanadium pentoxide (V2O5) particles were successfully prepared by spray pyrolysis (SP) in a precursor solution with an ammonium nitrate (NH4NO3) additive. The correlation between the porous structure and the electrochemical properties of the V2O5 particles was investigated. The porous structure markedly changed upon increasing the concentration of NH4NO3 in the precursor solution from 0 to 0.408 mol L−1. Pore structure analysis based on N2 adsorption-desorption isotherm measurements indicated that porous nanostructured V2O5 particles with a pore size of less than 100 nm can be prepared by the novel SP method and that an increase in the NH4NO3 concentration in the precursor solution can enlarge the pores in the V2O5 particles, especially those with a size between 20 and 80 nm. The porous nanostructured V2O5 prepared with an NH4NO3 concentration of 0.272 mol L−1 exhibited a first discharge capacity of 400 mAh g−1 at 20 mA g−1. The unique porous structure of V2O5 particles significantly enhanced the rate performance and exhibited a first discharge capacity of 180 mAh g−1 at 1200 mA g−1, which is much higher than that of dense V2O5 particles (70 mAh g−1).