Carbon-encapsulated nano-MnO composite with novel multiple structure loaded on N-doped carbon webs (CMNCWs) has been designed and fabricated by using polypyrrole webs as both template and precursor. As an anode material for lithium-ion batteries, CMNCWs exhibit a superhigh reversible capacity and excellent rate capability, delivering a capacity as high as 1268mAhg−1 after 700 cycles at a current density of 1.0Ag−1. Such superior electrochemical performance can be attributed to the unique multiple structure, which cannot only effectively shorten the transport path of Li+ ions and enhance the conductivity, but also relieve the volume change and prevent agglomeration of Mn grains during the phase transformation in the conversion reaction.