Constructing the nanostructure of transition metal oxides for high energy density lithium-ion batteries has been widely studied recently. Prompted by the idea that the transition metal can serve as a catalyzer influence on the reversibility of solid-electrolyte interphase films, Co/MnO@C composite nanofibers were designed by electrospinning and chemical vapor deposition methods. The Co/MnO@C electrode showed superior electrochemical performance with a large capacity increase for the first 400 cycles and a high rate performance of 1345 mA h g-1 at 1000 mA g-1. There was no obvious decay of capacity over the whole 1000 cycles, demonstrating the excellent cycling stability of the samples. The new design and synthesis of the anodic materials may offer a prototype for high-performance and strong-stability batteries.