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), Mössbauer 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 0.5–1μm. Test shows that the reversible capacity of spherical-like LiFePO₄ is about 140mAhg⁻¹ at 0.1C. The capacity fading is neglectable.