Cobalt oxide thin films composed of hollow spherical Co 3O 4 particles have been prepared by a two-step method. The first step involves in the synthesis of hollow cobalt alkoxide particles in a stable suspension from mixed polyalcohol solutions of cobalt acetate in oil bath at 170 °C. The second step includes the thin film fabrication by electrostatic spray deposition (ESD) and subsequent heat treatment in nitrogen. The obtained Co 3O 4 films with the unique hollow particle microstructure exhibit high reversible capacity of above 1000 mAh g -1 during up to 50 cycles and good rate capability. The films are promising negative electrodes for high energy lithium-ion batteries.