Based on the high theoretical capacity of Co3O4 for lithium storage, a noval type of monodisperse hollow carbon spheres with encapsulation of Co3O4 nanoparticles (HCSE-Co3O4) were designed and synthesized. The monodisperse hollow carbon spheres not only can provide enough void volume to accommodate the volume change of encapsulated Co3O4 nanoparicles, but also can prevent the formation of solid electrolyte interface (SEI) films on the surface of Co3O4 nanoparticles and following direct contact of Co and SEI films upon lithium extraction. The HCSE-Co3O4 electrode exhibit highly reversible capacity, excellent cycle performance and rate capability attributed to the unique structure. The reversible capacity of HCSE-Co3O4 electrode is as high as 500mAhg−1 at a current density of 744mAg−1, while that of bare Co3O4 electrode is only around 80mAhg−1.