CaCu3Ti4O12 ceramics doped with 0-2.0 wt% Li2CO3 were prepared by the solid-state reaction, and their electric and dielectric properties were investigated. It is found that these ceramics had the properties of high dielectric constant and comparatively low dielectric loss. At the doping amount of 0.5 wt%, the dielectric constant is kept to be 105 with weak frequency dependence below 105 Hz, and its loss tangent (tan δ) is suppressed below 0.1 between 300 Hz-5 kHz (with the minimum value of 0.06 at 1 kHz from 218 K to 338 K). The impedance spectroscopy analysis confirms that the decrease of dielectric loss is mainly due to the increase of resistance in the grain boundary, which may be related to the influence of Ti4O7 secondary phase. Our result indicates that doping Li2CO3 is an efficient method to optimize the dielectric properties of CaCu3Ti4O12.