In this study, we successfully design and synthesize the mesoporous carbon coated carbon nanofibers (CNF@mesoCs) for the Li-air battery. The composites are fabricated via electrospinning technique and nanocasting strategy. After mesoporous carbon coating process, the composites have retained their original one-dimensional structure as pristine carbon nanofibers. Every nanofiber entangles with each other to form a three-dimensional cross-linked web structure. Because of the mesoporous carbon coating on carbon nanofibers, the surface area increases from 708m(2) g(-1) to 2194m(2) g(-1). We confirm that the mesoporous carbon coated on carbon nanofibers is well-graphitized by analysis of Raman spectra. The graphitized surface of CNF@mesoCs (4.638 S cm(-1)) is believed to result in their higher electrical conductivity than that of pristine carbon nanofibers (3.0759 S cm(-1)). Without employment of any binders and metal foams, the cathode of CNF@mesoCs exhibits high discharge capacity of 4000 mAh g(-1), which is much higher than that from pristine carbon nanofibers (2750 mAh g(-1)). This work demonstrates that the fabricated CNF@mesoCs structures have a great potential to be employed as light-weight and efficient electrode for energy storage and conversion devices. (C) 2014 Elsevier B.V. All rights reserved.