Spherically shaped vanadium pentoxide (V 2 O 5 ) cathode powders with porous or dense morphologies are prepared directly via spray pyrolysis by varying the preparation temperatures between 600 and 1000°C. The powders prepared at 600°C consist of nanometer-sized rod-shaped crystals with porous structures. The V 2 O 5 powders prepared at 1000°C have spherical shapes, clean surfaces, and dense structures, because of complete melting of the powders that occurs inside the hot-wall reactor. The Brunauer–Emmett–Teller (BET) surface areas of the V 2 O 5 powders decrease from 24.7 to 3.2m 2 g −1 when the preparation temperature increases from 600 to 1000°C. The V 2 O 5 powders prepared at 1000°C have better cycle properties than those prepared at 600 and 800°C. The discharge capacity of the V 2 O 5 powders prepared at 1000°C decreases from 432mAhg −1 to 263mAhg −1 after 20 cycles, in which the capacity retention is 61%.