Spinel LiCoxMn2-xO4 powders were prepared by sol-gel combined with heating treatment process. The structure, morphology and electrochemical properties of LiCoxMn2-xO4 powders were characterized by XRD, TEM and constant current charge/discharge techniques. The results show that lattice constant and crystal size of LiCoxMn2-xO4 powder decrease and the crystal aberrance increase with the increasing of cobalt content which has less effect on its spinel structure. The initial discharge special capacity of LiCoxMn2-xO4 decreases slightly with the increasing content of Co but its cyclic performance is improved obviously resulted from the improvement of structure stability. Comprehensively the special capacity and the cycle performance, LiCo0.1Mn1.9O4 composed of about 80nm particles exhibits superior electrochemical property and may be used as the cathode material in new type Li-ion battery.