LiCoO2 spinel is one of the most promising cathode materials for Li-ion batteries. However, the capacity fading is aggravated at high voltage, resulting from cathode degradation and electrolyte decomposition owing to over-charging. To improve structural stability, surface modification is an effective method. In this study, nano-crystallized ZnO was coated on the surface of commercial LiCoO2 powders via sol-gel method. The correlation among the amount of coated ZnO, microstructure of modified cathode and the cycling behavior of surface-treated LiCoO2 powders is discussed. Moreover, the effects of cycling for cathodes with as-derived powders on the phase and morphology are also considered. The surface morphology observed from the scanning electron microscope (SEM) images shows that nano-crystallized and spherical ZnO particles with an average size of about 20 nm have developed after coating. The size of ZnO nanocrystallites is related to the initial concentration of Zn2+ cations. In comparing the characteristics of bare and coated LiCoO2 powders, improvement in cyceability of the ZnO-coated cathode is explored. It is confirmed that Zn2+ ions diffuse into the surface region of LiCoO2 particles. To reveal the effects of Zone coating on enhancing the electrochemical properties of LiCoO2 cathode during charge and discharge, the morphological differences between the cathode material before and after cycling are discussed.