3D hierarchical SnS2 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 SnS2 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 264 mAh g(-1) at 1C (0.65 A g(-1)). 5C, and 10C rate, respectively. Such outstanding performance of these SnS2 microspheres is ascribed to their unique 3D hierarchical structures. The new charge-discharge mechanism of 3D SnS2 microsphere as anode in Li-ion battery is further revealed. (C) 2010 Elsevier B.V. All rights reserved.