Hollow SiO2 microspheres coated with a nitrogen doped carbon layer are synthesized by using poly(acrylic acid) as a hollow structure template and dopamine as a carbon source. Based on a facile self-polymerization reaction, nitrogen doped carbon layer can be easily formed on the surface of hollow SiO2 microspheres, which can effectively increase the electronic conductivity of anode material. Moreover, the hollow structure and N doped carbon layer can improve lithium ion diffusivity and accommodate volume change of SiO2 anode simultaneously and hence exhibits excellent rate capabilities and superior cycling stability. For example, a high reversible specific capacity of 587 mA h g−1 can be remained at a current density of 1.0 A g−1 after 600 cycles, with 0.03% decade each cycle.