The aniline was polymerized onto functionalized multi-walled carbon nanotubes in order to obtain a cathode material with core-shell structures for lithium batteries. The structure and morphology of the samples were investigated by Fourier transform infrared spectroscopy analysis, scanning electron microscope, transmission electron microscope and X-ray diffraction. The electrochemical properties of the composite were characterized by the cyclic voltammetry, the charge/discharge property, coulombic efficiency, and ac impedance spectroscopy in detail. At a constant current density of 0.2 C, the first specific discharge capacity of the reduced and oxidized PANI/WMCNTs were 181.8 mAh/g and 135.1 mAh/g separately, and the capacity retention rates were corresponding to 76.75% and 86.04% for 100 cycles with 99% coulombic efficiency. It was confirmed that the CNTs obviously enhanced the conductivity and electrochemical performance of polyaniline, and compared with the pure PANI, the reduced composite possessed a quite good performance for the cathode of lithium batteries.