Cobalt oxide thin films composed of hollow spherical Co3O4 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 Co3O4 films with the unique hollow particle microstructure exhibit high reversible capacity of above 1000mAhg−1 during up to 50 cycles and good rate capability. The films are promising negative electrodes for high energy lithium-ion batteries.