Hierarchically porous materials are an ideal material platform for constructing high performance Li-ion batteries (LIBs), offering great advantages such as large contact area between the electrode and the electrolyte, fast and flexible transport pathways for the electrolyte ions and the space for buffering the strain caused by repeated Li insertion/extraction. In this work, NiO microspheres with hierarchically porous structures have been synthesized via a facile thermal decomposition method by only using a simple precursor. The superstructures are composed of nanocrystals with high specific surface area, large pore volume, and broad pore size distribution. The electrochemical properties of 3D hierarchical mesoporous NiO microspheres were examined by cyclic voltammetry and galvanostatic charge-discharge studies. The results demonstrate that the as-prepared NiO nanospheres are excellent electrode materials in LIBs with high specific capacity, good retention and rate performance. The 3D hierarchical mesoporous NiO microspheres can retain a reversible capacity of 800.2 mA h g(-1) after 100 cycles at a high current density of 500 mA g(-1).