A novel LiFePO4/C composite with 3D carbon network was prepared using Cetyltrimethyl Ammonium Bromid (CTAB) and starch as carbon sources via a facile method. The 3D carbon network structure was composed of a full and uniform carbon coating and a continuous carbon film framework. Good conductive paths enhancing electrons transfer efficiency and porous structure facilitating diffusion of lithium ions have been constructed by the 3D conductive network structure, which contributes the high ionic and electrical conductivities. As a result, the LiFePO4/C composite possesses an excellent electrochemical performance especially the high-rate cyclic performance. It delivers a capacity of 95mAhg−1 at current density of 3.4Ag−1 (20C). After 1200 cycles, the discharge capacity of 74mAhg−1 can still be obtained, almost reaching a retention of 80%, which is higher than the best cyclic performance in previous investigations.