N-doped coaxial CNTs@α-Fe2O3@C nanofibers have been successfully synthesized according to a facile solvothermal/hydrothermal method. The obtained CNTs@α-Fe2O3@C nanofibers composites exhibited special three-dimensional (3-D) network structure, which endows they promising candidate for anode materials of lithium ion battery. The coaxial property of CNTs@α-Fe2O3@C nanofibers could significantly improve the cycling and rate performance owing to the acceleration of charge/electron transfer, improvement of conductivity, maintaining of structural integrity and inhibiting the aggregation. The α-Fe2O3 nanoparticles with small size and high percentage of N-doped amount could further improve the electrochemical performance. As for the CNT@α-Fe2O3@C nanofibers, the capacity presented a high value of 1255.4 mAh/g at 0.1 C, and retained at 1213.4 mAh/g after 60 cycles. Even at high rate of 5 C, the capacity still exhibited as high as 319 mAh/g. The results indicated that the synthesized N-doped coaxial CNTs@α-Fe2O3@C nanofibers exhibited high cycling and rate performance.