▶ The phase transformation and performance of LiFePO4 materials are reviewed. ▶ Carbon coating is more critical than doping and particle size control. ▶ Iron deposit on graphite anode leads to capacity degradation. ▶ Low temperature performance can be improved by electrolyte modification. LiFePO4 has been considered a promising battery material in electric vehicles. However, there are still a number of technical challenges to overcome before its wide-spread applications. In this article, the structure and electrochemical performance of LiFePO4 are reviewed in light of the major technical requirements for EV batteries. The rate capability, capacity density, cyclic life and low-temperature performance of various LiFePO4 materials are described. The major factors affecting these properties are discussed, which include particle size, doping, carbon coating, conductive carbon loading and synthesis techniques. Important future research for science and engineering is suggested.