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The effects of tungsten W doping and coating on the electrochemical performance of LiCoO2 cathode are compara-tively studied in this work. The amount of modification component is as low as 0.1 wt％and 0.3 wt％respectively. After 100 cycles between 3.0 V–4.6 V, 0.1 wt％W doping provides an optimized capacity retention of 72.3％. However, W coating deteriorates battery performance with capacity retention of 47.8％, even lower than bare LiCoO2 of 55.7％. These different electrochemical performances can be attributed to the surface aggregation of W between doping and coating methods. W substitution is proved to be a promising method to develop high voltage cathodes. Practical performance relies on detailed synthesis method.