LiFePO₄/C particles with different LiFePO₄–C interface were prepared and investigated with emphasis on the interface property which has been found to be important for the power performance of LiFePO₄. Soft-X-ray-absorption (XAS) spectra collected at O and C K-edge show a distinct bonding character between carbon and LiFePO₄ in carbon coated LiFePO₄/C. Galvanostatic change-discharge at different rates and electrochemical impedance tests demonstrate that the interface action between LiFePO₄ and carbon within LiFePO₄/C composites has a crucial effect on its electrochemical performance.