LiFePO4/carbon nanowires with three-dimensional (3D) nano-network structure were successfully synthesized via evaporative self-assembly method induced by amylose. The morphologies and structures are investigated by X-ray diffractometer, scanning electron microscope and transmission electron microscope. The co-axis one-dimensional LiFePO4/C nanowires, which are 50nm in diameter and between 400nm and 1μm in length, are tightly connected into 3D nano-network structure by the amorphous carbon from the short branched chains of amylase. They deliver high capacities of 167 and 138mAhg−1 at 0.1C and 50C respectively. After 100 cycles at 50C rate, the capacity retention of the composite can still maintain 92.8% (128mAhg−1).The unique 3D nano-network structure can effectively increase the contact between active materials and electrolyte, and improve the poor electronic and ionic conductivity.