Lithium cobalt oxide powders have been successfully prepared by a molten-salt synthesis (MSS) method using a eutectic mixture of LiCl and Li2CO3 salts. The physico-chemical properties of the lithium cobalt oxide powders are investigated by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), particle-size analysis and charge–discharge cycling. A lower temperature and a shorter time (∼700°C and 1h) in the Li:Co=7 system are sufficient to prepare single-phase HT-LiCoO2 powders by the MSS method, compared with the solid-state reaction method. Charge–discharge tests show that the lithium cobalt oxide prepared at 800°C has an initial discharge capacity as high as 140mAhg−1, and 100mAhg−1 after 40 cycles. The dependence of the synthetic conditions of HT-LiCoO2 on the reaction temperature, time and amount of flux with respect to starting oxides is extensively investigated.