Novel hollow flower-like SnO structures have been successfully synthesized by using a facile solvothermal method approach, which injecting LiN(SiMe3)2 to the solution of SnCl2 and oleamine. The as-synthesized hollow flower-like SnO structures were aggregated by ultrathin SnO nanosheets with large surface area and exhibit narrow size distribution of ~2.0 µm. The electrochemical performance of hollow flower-like SnO structures were examined as an anode material in coin cells for lithium-ion batteries. It demonstrates excellent lithium ion batteries performance as characterized by the cycling stability, specific capacity, cyclic voltammetry and rate performance. The measured discharge capacity is 361.4 mAh g-1 after 50 charge/discharge cycles with 46% capacity retention, which indicated a improving in cyclic stability. This result demonstrated that the specific hollow structure has great potential as the electrodes for lithium ion batteries. This work may provide an attractive road to synthesize other hollow-flower structures of transition metal oxides.