LiFePO4 is one of the most promising cathode materials for Li-ion batteries. However, its low electronic conductivity and slow Li-ion diffusion rate lead to poor electrochemical performance, especially poor rate performance. The hybrid of LiFePO4/Nitrogen and Sulfur co-doped graphene is successfully synthesized via a self-assembly method. Given its Nitrogen and Sulfur co-doped graphene matrix, the hybrid exerts a significantly impact on the electron conductivity of LiFePO4, resulting in excellent electrochemical properties and power density. The LiFePO4 composite has reversible capacity of 106.1 mAhg −1 at 10 C and 94.6 mAhg−1at 15 C. Moreover, with less than 5% loss of discharge capacity after 500 cycles at 10 C, the Nitrogen and Sulfur co-doped graphene can effectively improve the electrochemical performance of LiFePO4.