A very simple and rapid method for synthesizing LiFePO4-C composite has been developed by vibrant type ball-milling for 30min and microwave heating for 2–4min. X-ray diffraction and Mössbauer spectroscopy verify that well-crystallized LiFePO4 without Fe3+ impurities is obtained. From laser particle size analysis and transmission electron microscopy, it is confirmed that a LiFePO4-C composite with fine and uniform particle size (mean particle size ≤0.640μm, D75 in volume distribution ≤0.592μm) and with extremely uniform carbon distribution is prepared by vibrant type ball-milling and microwave heating. The LiFePO4-C delivers a high initial discharge capacity of 161mAhg−1 at C/10 and shows very stable cycling behaviour.