The surface conditions of LiFePO4 powder were modified by adding AlF3 and Al2O3 by using the sol-gel process to improve its electrochemical properties. The surface of LiFePO4 powders was partially covered with nano-sized AlF3 and Al2O3, which is confirmed by using a transmission electron microscope image. The states of coated Al materials were examined by using X-ray photoelectron spectrometer results. The nano-sized AlF3- and Al2O3-coated LiFePO4 powders showed no difference in the bulk structure compared with the pristine one. However, the AlF3- and Al2O3-coating on LiFePO4 powders improved the overall electrochemical properties such as the discharge capacity, the cyclability, and the rate capability compared with those of a pure LiFePO4. Such enhancements were attributed to the presence of a stable AlF3 and Al2O3 layer which acts as an interfacial stabilizer on the surface of LiFePO4 powders.