Multihollow LiFePO4 was prepared by firing a solid mixture resulting from evaporation of aqueous solution containing emulsifier-free poly(styrene-methyl methacrylate-acrylic acid) latex microspheres and precursors of Li+, Fe2+, and PO43-. X-ray diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy were employed to characterize the crystallization, microstructure, and the purity of the resultant powders. Because of the multihollow microstructure and conductive carbon, LiFePO4 showed superior electrochemical properties. Sample prepared at 700 degrees C exhibited small polarization at high scan rate of 0.5 mV/s during cyclic voltammetry measurement, and delivered capacity close to its theoretic value below 1 mA/cm(2) (similar to 1.2 C) and showed capacity more than 100 mAh/g at a high current density of 5 mA/cm(2) (similar to 6 C) and at room temperature. (c) 2005 The Electrochemical Society. All rights reserved.