3D hierarchical SnS 2 microspheres have been designed and fabricated via a one-pot biomolecule-assisted hydrothermal method. When used as anode material in rechargeable Li-ion batteries, the as-formed SnS 2 microspheres self-assembled by layered nanosheets, show high lithium storage capacity, long-term cycling stability and superior rate capability. After charge–discharge for 100 cycles, the remaining discharge capacities are kept as high as 570.3, 486.2, and 264mAhg −1 at 1C (0.65Ag −1 ), 5C, and 10C rate, respectively. Such outstanding performance of these SnS 2 microspheres is ascribed to their unique 3D hierarchical structures. The new charge–discharge mechanism of 3D SnS 2 microsphere as anode in Li-ion battery is further revealed.