Hollow Mo2C@C core-shell nanofibers (H-Mo2C@C/NFs) have been successfully synthesized via an integrated procedure including coaxial electrospinning, oil extraction and carbonization. As an anode of lithium-ion batteries, H-Mo-2 C@C/NF's delivers high discharge capacity of 1176.3 mA h g(-1) in the first cycle at a current density of 0.1 A g(-1 )and exhibits good rate capability and reversibility. The capacity can maintain at 595.1 mA h g(-1) even when the current density is up to 5 A g(-1). In addition, at a high current density of 1 A g(-1) , H-Mo2C@C/NF's also displays extraordinary long-term cycling performance with a capacity of 674.4 mA h g(-1). The excellent rate performance and cycling stability result from the synergistic effect of Mo2C nanoparticles and hollow structure nanofiber matrix. Coaxial electrospinning technology can be widely extended to manufacture other metal carbide/carbon composites to achieve important energy storage and other applications.