Spherical-like LiFePO4 was synthesized by hydrothermal synthesis method using Phenanthroline as a complexing-agent to avoid the Fe(II) ions from oxidation and control the growth of the crystal. Structural, electron valence state, morphology and particle size were investigated by X-ray diffraction (XRD), X-ray photoelectron spectra (XPS). Mossbauer spectra, scanning electron microscopy (SEM) and laser particle sizer. Charge-discharge cycling performances were used to characterize its electrochemical properties. The sample possesses uniformly distributed spherical-like particles with an average size of 0.5-1 mu m. Test shows that the reversible capacity of spherical-like LiFePO4 is about 140 mAh g(-1) at 0.1 C. The capacity fading is neglectable. (C) 2008 Published by Elsevier B.V.