LiFePO4/C composite was synthesized at 600°C in an Ar atmosphere by a soluble starch sol assisted rheological phase method using home-made amorphous nano-FePO4 as the iron source. XRD, SEM and TEM observations show that the LiFePO4/C composite has good crystallinity, ultrafine sphere-like particles of 100–200nm size and in situ carbon. The synthesized LiFePO4 could inherit the morphology of FePO4 precursor. The electrochemical performance of the LiFePO4 by galvanostatic cycling studies demonstrates excellent high-rate cycle stability. The Li/LiFePO4 cell displays a high initial discharge capacity of more than 157mAhg−1 at 0.2C and a little discharge capacity decreases from the first to the 80th cycle (>98.3%). Remarkably, even at a high current density of 30C, the cell still presents good cycle retention.