Olivine-type, orthorhombic, LiFePO4 powders with small particle size have been successfully synthesized by the emulsion-drying method. The electronic and crystal structure is analyzed by X-ray absorption spectroscopy (XAS) and X-ray diffraction Rietveld refinement. The powder calcined at 750 degreesC shows the highest discharge capacity of 125 mAh g(-1) with excellent cycle stability. The discharge capacity of this powder increases to 154 mAh g(-1) on increasing the addition of carbon black as a conductive agent up to 40 wt.%. In a rate capability test, the discharge capacity is completely recovered and retained up to the 700th cycle. (C) 2004 Elsevier B.V. All rights reserved.