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°C shows the highest discharge capacity of 125mAhg−1 with excellent cycle stability. The discharge capacity of this powder increases to 154mAhg−1 on increasing the addition of carbon black as a conductive agent up to 40wt.%. In a rate capability test, the discharge capacity is completely recovered and retained up to the 700th cycle.