The size- and shape-controlled synthesis of Sb(2)S(3) nanostructures has been successfully realized by a facile hydrothermal route. A range of dimensional nanostructures, such as one-dimensional nanorods, two-dimensional nanowire bundles, three dimensional sheaf-like superstructures, dumbbell-shaped superstructures, and urchin-like microspheres, could be obtained through introducing different organic complex reagents or ionic liquids to the reaction system. The formation mechanisms of various Sb(2)S(3) nanostructures have been rationally proposed based on the crystal structure and the nature of the complex reagents and the ionic liquid. The effects of experimental parameters on the final product are also discussed in detail. In addition, electrochemical measurements demonstrate that the as-synthesized Sb(2)S(3) nanostructures have higher initial Li intercalation capacity and excellent cyclic performances, which indicates that the as-synthesized Sb(2)S(3) nanostructures could have potential applications in commercial batteries.