The precursors of a LiCoO₂ powder were synthesized from the hydroxides LiOH and Co(OH)₂ as starting materials at various temperatures by precipitation process and freeze-drying in this study. The LiCoO₂ samples were calcined at 800 ℃ in a short time (2 hours). Measurements of XRD and SEM were performed to characterize the properties of the prepared materials. Finally, The structure of HT-LiCoO₂ was simulated by the commercial software Creius²(Molecular Simulations, Inc.) from the results of Rietveld analysis.