V2O5 microparticles of 0.3-0.6 μm in diameter were prepared from VO(O-C3H7 i)3 in an ethanol solution by the sol-gel method. The addition of poly(ethylene glycol) and acetyl acetone into the sols was effective to control the size and spherical shape of V2O5 particles. The particles thus obtained were amorphous having a layered structure with hydrated water, and transformed into an orthorhombic phase at 500°C through a glassy state. The microparticles were positively charged in I2-containing acetone, so that they were electrophoretically deposited on the cathode with applied DC voltage. The prepared particles were used as a cathode in an electrochemical cell with a lithium metal as an anode. Discharge capacity of a rechargeable cell of Li / LiPF6 (ethylene carbonate + diethylene carbonate) / V2O5 -based composite was 110-180 mAh g-1 when the potential range and current density were 2-4 V and 0.1 mAcm-2, respectively.