A polymer-pyrolysis method was used to synthesize LiNi0.8Co0.2O2, which has potential application in lithium ion batteries. The effect of calcination temperature and time on the structure and electrochemical performance of the material was investigated. XRD analysis showed that the powders obtained by calcination at 750°C for 3h had the best-ordered hexagonal layer structure. SEM image showed these powders were fine, narrowly distributed with platelet morphology. The charge–discharge tests demonstrated these powders had the best electrochemical properties, with an initial discharge capacity of 189mAh/g and capacity retention of 95.2% after 50 cycles when cycled at 50mA/g between 3.0 and 4.3V. Besides, these powders also had exhibited excellent rate capability.