Co3O4 is a good anode candidate for high-performance lithium ion batteries (LIBs), attributed to its high specific capacity. However, due to its poor conductivity and significant volume expansion during electrochemical reactions, electrochemical performance of Co3O4 electrode is quite poor for practical applications. Co3O4 electrodes with various micro-/nanostructures have been designed and synthesized but their performances are still unsatisfied. In this study, we propose and develop a novel sandwich type of Co3O4 nanostructures by adjusting the ratio of ammonium fluoride and urea during hydrothermal reactions. When this sandwich-like Co3O4 composite electrode was used as the electrode for LIBs, it retained an outstanding reversible capacity of 857 mAh g−1 after 70 cycles at a current density of 500 mA g−1. When the current density was increased to 1000 mA g−1, the reversible capacity was kept at 865 mAh g−1 with insignificant changes of its capacity.