Layered LiCoO2 as a cathode material for rechargeable lithium battery is prepared using the acetate self-mixing method. Using this method, the preparation procedure consists of just two steps: spontaneous and homogeneous mixing of molten acetates at 80°C, as well as direct thermal reaction at high temperature without any pulverization, grinding, agglomeration, particle morphology controlling, particle size controlling, and even artificial stirring of reactants. When lithium and cobalt acetates are exposed to the temperature of 80°C, they can be fluidized substances by themselves without any solvents and spontaneously mixed together. In this way, layered LiCoO2 phase is prepared by just simple heat treatment. The heating at 350°C is interposed to accomplish steady intermediate phase translation without any intermittent cooling. The 7Li MAS NMR and Raman spectra upon the thermal exposure of the reactants demonstrate the feature of the spontaneous mixing process of the molten reactants. The LiCoO2 prepared by the acetate self-mixing method show quite prospective properties as a cathode material for lithium rechargeable battery, an initial discharge capacity of 149.5mAh/g and the discharge capacity retention of 98.9% and 97.5% after 10 and 20 cycles, respectively.