Inspired by the structure of peapod, MnO@C hybrid with internal void space has been prepared. In this bionic structure, the MnO nanoparticles are separated and confined in a conductive carbon sheath that leaves enough room for expansion and contraction during lithiation/delithiation process. Such peapod-like MnO@C can address the issues related to MnO dissolution, pulverization, and aggregation. As a result, the sample demonstrates superior electrochemical performances in terms of high reversible capacity, excellent high-rate capability, and good cyclability.