A spray-drying method has been developed to synthesize a molecularly mixed precursor from which ultrafine LiCoO2 powder is prepared by sintering in a short time. Measurements of DTA/TGA, IR, XRD, SEM and reversible capacity are performed to characterize the properties of the prepared materials. The obtained powder is HT-LiCoO2 with an α-NaFeO2 structure. It is homogeneous with a grain size in the order of hundreds of nanometers. The electrochemical properties are good, viz., an initial charge capacity of 148 mA h g−1, a discharge capacity of 135 mA h g−1, and satisfactory cycle-life. The commercial prospects of this novel technique are promising.