Crystalline Co3O4 powders with controllable morphology have been prepared using cobalt chloride and various alcohol precursors at different temperatures. The non-aqueous precursor is examined by simultaneous differential thermal analysis (DTA) and thermogravimetric analysis (TGA), and the obtained powders are characterized by X-ray diffraction (XRD) and scanning electronic microscopy (SEM). Co3O4 particles demonstrate a dramatic tetragonal dipyramid structure when synthesized from benzyl alcohol and cobalt chloride. A stable and reversible storage capacity for lithium of 740mAhg−1 within 50 cycles is achieved on electrochemical performance testing.