The NiO doped LiFePO4/C composite was synthesized by a simple solid state method. The structure and morphology of synthesized particles were characterized by XRD, Raman spectrum, SEM, TEM and EDS. Electrochemical performance of the pristine and nickel oxide modified samples was evaluated by galvanostatic charge-discharge test, CV, and EIS. The results indicate that NiO doped LiFePO4/Li type coin cell exhibits improved specific capacity and cycle stability, especially at high rates. Among all the modified samples, the 5.0%wt NiO doped sample shows the best electrochemical performance, which achieves a specific capacity of 129mAhg−1 at 1C current rate due to the modest graphitization of carbon layer on the surface of LiFePO4 particles. The results indicate that nickel oxide modification is an effective way to improve the electrochemical performance of LiFePO4/C cathode materials for lithium ion batteries.