A novel CdO and carbon co-coated LiFePO4 (LFP) cathode material has been synthesized, and the effect of CdO on the physicochemical properties and electrochemical performance has been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-Ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), transmission electron microscopy (TEM) and electrochemical measurements. The results show that the LFP/(C+CdO) particles are coated with a mixed layer (about 2 similar to 3 nm) combined by amorphous carbon and CdO. Compared to the LFP/C electrode, the capacity retention ratio and high C-rate performance for LFP/(C+CdO) have been effectively improved, which is due to the enhanced structural stability, the reduced charge-transfer resistance, and the increased electronic conductivity. Therefore, the CdO and carbon co-coating is an effective surface modification technique. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.014301jes] All rights reserved.