Mesoporous Li 4 Ti 5 O 12 /carbon nanofibers (LTO/C NFs) are prepared by a facile electrospinning method combined with soft-template self-assembly. The morphology and structure are characterized by field-emission scanning electron microscopy, transmission electron microscopy and X-ray diffraction. The diameter of as-prepared LTO/C NFs is approximately 400nm with highly crystallinity LTO nanoparticle completely embedded in carbon framework. Nitrogen adsorption–desorption isotherms and corresponding pore size distribution reveal that the mesoporous LTO/C NFs exhibite high specific surface area (212.1 m 2 /g −1 ) and large pore volume. Compared with the regular LTO/C NFs, the mesoporous LTO/C NFs show much higher rate capability and better capacity retention. At a current rate of 5 C, the reversible capacity of the mesoporous LTO/C NFs electrode is up to 127.4 mAh g −1 and still remains at 122.7 mAh g −1 after 100 cycles. The excellent electrochemical performances are closedly related to well-defined one-dimensional (1D) mesoporous nanostructure with LTO nanoparticles embedded in the carbon framework, which efficiently shortened the path length of Li + diffusion, enhanced electrolyte-active material contact area and facilitated rapid electron transfer.