LiFePO4 and LiFePO4/C microspheres are successfully synthesized via facile co-precipitation in an elevated temperature oil bath. Their morphologies and structures are investigated by X-ray diffractometer, scanning electron microscope and transmission electron microscope. LiFePO4/C microspheres are uniform between 2 and 4μm in diameter and composed of nanoparticles from 30 to 80nm in size. Nanoparticles are coated by a thin nano-carbon layer and imbedded into three-dimensional nano-carbon networks. LiFePO4/C microspheres exhibit a high tap density (1.82gcm−3), deliver large reversible discharge capacity of 165mAhg−1 at 0.1C rate, excellent rate capability of 106mAhg−1 at 50C rate, and capacity retention over 98% after 20 cycles even applied 50C rate. Therefore, the material is a potential candidate for high-power lithium ion batteries.