The low-temperature electrochemical performance of LiFePO4/C cathode with 3D conducting networks is reported. XRD results show the sample is olivine-type structure. SEM and TEM images indicate that the particles consist of nanocrystalline LiFePO4 and are coated by nanocarbon webs and form conducting 3D networks. The 3D networks contained two effectively mixed conducting networks, one on the nanoscale and the other on the microscale. It is useful to shorten the distance of Li+ diffusion and e(-) transport and to improve the electrochemical performance. The LiFePO4/C cathodes show excellent capacity retention and cycling performance at -20 degrees C for lithium-ion batteries.