In the present study, an attempt is made to synthesis LiNi0.8Co0.2O2 compounds by adopting a novel solution combustion route, because this compound is a promising candidate to replace commercial LiCoO2 in secondary lithium batteries. LiNi0.8Co0.2O2 is synthesized at 750°C for 3, 12 and 24h in an air atmosphere. Its structural and electrochemical properties are characterized by means of X-ray diffraction (XRD), cyclic voltammetry, and charge–discharge studies. The charge–discharge behaviours suggests that the initial discharge capacities are different for different charging cut-off voltages. LiNi0.8Co0.2O2 shows high specific discharge capacity and good cycle-life performance.