Nitrogen-doped mesoporous carbon hollow spheres (N-MCHSs) were prepared using mesoporous silica hollow spheres as template and dopamine as carbon precursor. The N-MCHSs demonstrate high specific surface area and vegetable sponge-like mesoporous shell with interconnected “carbon bridges”, facilitating continuous electron transport and Li ion diffusion, and making the whole structure more stable. The influence of N contents and N-bonding configuration on the Li storage of N-MCHSs is discussed. The N-MCHSs carbonized at 800 °C demonstrate high reversible capacity and excellent rate performance, delivering a capacity of 485 mAh g−1 at a current of 0.5 A g−1 after 1,100 cycles. Even up to 4.0 A g−1, a high capacity of 214 mAh g−1 can be remained. The high electrochemical performance of N-MCHSs can be ascribed to mesoporous carbon hollow spheres structure and high level pyridinic nitrogen doping.