Three-dimensional foam structure LiFePO 4 /C composite has been successfully synthesized via evaporative self-assembly assisted by polyethylene glycol. The morphologies, structures and properties of bare LiFePO 4 and LiFePO 4 /C are investigated by X-ray diffractometer, scanning electron microscope, and transmission electron microscope. LiFePO 4 /C composite exhibits high capacity of 150mAhg −1 at the 1C rate, and excellent rate performance (120mAhg −1 at the 20C rate). The improved properties can be attributed to a unique three-dimensional foam structure constructed by facile evaporative self-assembly. Furthermore, the unique structure can increase the electrochemical reaction surface, enhance the electrochemical conductivity and promote lithium ion diffusion.