Nano- and micro-scaled LiFePO4 was synthesized by hydrothermal synthesis method using disodium ethylenediamine tetraacetate (Na2EDTA)-assisted to avoid the Fe(II) ions from oxidation and control the growth of the crystal. The as-synthesized samples were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), The SEM showed that the pH value of the synthesis solution played a key role in the formation of the ﬁnal products with different morphologies. Charge–discharge cycling performances were used to characterize its electrochemical properties. The results indicated that the nano-sized LiFePO4 presents enhanced discharge capacities (148 mAhg−1 at 0.1C-rate) and stable cycling performance. This study offered a simple method to design and synthesis nano-sized cathode materials for lithium-ion batteries.