A carbon-coated nanocrystalline LiFePO4 cathode material was synthesized by pyrolysis of polyacrylate precursor containing Li+, Fe3+ and PO4 −. The powder X-ray diffraction (XRD) and high-resolution TEM micrographs revealed that the LiFePO4/C composite as prepared has a core-shell structure with pure olivine LiFePO4 crystallites as cores and intimate carbon coating as a shell layer. Between the composite particulates, there exists a carbon matrix binding the nanocrystallites together into micrometer particles. The electrochemical measurements demonstrated that the LiFePO4/C composite with an appropriate carbon content can deliver a very high discharge capacity of 157mAhg−1 (>92% of the theoretical capacity of LiFePO4) with 95% of its initial capacity after 30 cycles. Since this preparation method uses less costly materials and operates in mild synthetic conditions, it may provide a feasible way for industrial production of the LiFePO4/C cathode materials for the lithium-ion batteries.