In this work, the mesoporous LiFePO4@C nanofibers have been successfully fabricated through a facile electrospinning method. The structure, morphology, chemical composition and lithium storage performance have been systematically investigated. The results reveal that the LiFePO4 grains with particle size of 15 nm are uniformly dispersed in the mesoporous carbon nanofibers. The LiFePO4@C electrode presents a high reversible capacity and excellent rate performance. It delivers a discharge capacity of 107 mAh g(-1) and retains 105 mAh g(-1) over 200 cycles at 10C. The excellent electrochemical performances are attributed to the novel nanostructure where LiFePO4 nanoparticles are embedded in the carbon fibers. This designed structure can significantly enhance the conductivity of LiFePO4@C, accelerate the diffusion of electrolyte, and thus facilitate the transport of electrons and Li-ions.