ZrO2 nanolayer coated LiFePO4 particles were successfully prepared by a chemical precipitation method. Nanolayer structured ZrO2 was found on the surface of LiFePO4 particles by high resolution transmission electron microscopy (HRTEM). The coating does not affect the crystal structure of the LiFePO4 core, as determined by X-ray diffraction (XRD) and selected area electron diffraction (SAED) on individual particles. The ZrO2 coating can remarkably improve the electrochemical performance at high charge/discharge rate. This improvement may be due to the amelioration of the electrochemical dynamics on the LiFePO4 electrode/electrolyte interface resulting from the effects of the ZrO2 nanolayer coating.