Three-dimensional (3D) hollow nanostructure has been intensively investigated for preparing desirable anode material. Herein, VN hollow spheres are made up of porous nanosheets which were prepared through a one-step solvothermal route and followed with calcination process under ammonia atmosphere. Consequently, the obtained hollow sphere structure can provide large surface area and exhibiting unprecedented stable long cycling performance (456 mA h g−1 after 1100 cycles), when applied as an anode for lithium intercalation. Besides, the anode material also demonstrates a high capacitive contribution of 76.1% at 2 mV s−1 for the total charge.