LiFePO4, doped LiM x Fe1−x PO4, and Li1−x M x FePO4 compounds have been prepared via a sol–gel synthesis method. The physical properties of the as-prepared lithium iron phosphates were characterised by X-ray diffraction, X-ray absorption near-edge spectroscopy (XANES), and magnetic susceptibility. The electrochemical properties lithium iron phosphates were tested by a variety of electrochemical techniques. Lithium iron phosphate electrodes demonstrated a stable discharge capacity of 160–165mAhg−1, almost approaching the theoretical capacity. The good electronic conductivity and nanocrystalline could contribute to the unique performance of lithium iron phosphate electrodes. Lithium iron phosphates have a significant potential to be used as a new cathode materials in Li-ion batteries.