The LiCo1-xSbxO2 (0<x<1) materials were prepared for the first time. Comparing with parent LiCoO2 sample, they show improved cycleability under higher upper limit potential, better rate capability and thermal stability. XRD, SEM and particle size analysis indicate that the introduction of Sb during preparation effectively suppress the particle growth and thus the “doping” phase shows reduced particle size. Moreover, XPS measurements tell that the added Sb is enriched in the layer near the particle surface. According to these observations, it is reasonable to believe that the mechanism of the performance improvement is attributed to some coating effect for LiCo1-xSbxO2 materials.