A novel method has been employed to synthesize layered LiNi0.8Co0.2O2 cathode material by calcination of Ni–Co hydroxide–carbonate precursor prepared by a route involving separate nucleation and aging steps (SNAS) together with LiOH under air atmosphere. Thermogravimetry (TG) and differential thermal analysis (DTA) combined with on-line evolved gas mass spectrometry (EGMS) analysis were employed to study the reaction process. The synthesized material was characterized by means of X-ray diffraction (XRD), laser particle size distribution analysis, field emission scanning electron microscope (FE-SEM) and galvanostatic charge/discharge cycling. The synthesized LiNi0.8Co0.2O2 presents a narrow distribution of submicron-sized particles and exhibits a good electrochemical property with initial discharge specific capacity of 194.8mAhg−1 in the voltage range 2.75–4.5V (versus Li/Li+). The novel method for the preparation of submicron-sized LiNi0.8Co0.2O2 material has the particular advantage of simple synthesis process and low synthesis cost.