The precursors of LiFePO4 were prepared by low heating solid-state coordination method using lithium acetate, ammonium dihydric phosphate, ferrous oxalate and citric acid as raw materials. Olivine phase LiFePO4 as a cathode material for lithium-ion batteries was successfully synthesized by microwave heating in a few minutes. X-ray diffraction (XRD) and transmission electron microscope (TEM) were used to characterize its structure and morphology. Cyclic voltammetry (CV) and charge–discharge cycling performance were used to characterize its electrochemical properties. The results showed that the grain size of the optimal sample was about 40–50nm, and the as-prepared particles were homogeneous. The nano-sized LiFePO4 obtained has a high electrochemical capacity (125mAhg−1) and stable cycle ability.