The large scale formation of uniform Sb₂S₃ nanorod-bundles has been achieved via a simple and mild hydrothermal approach with the assistance of polyvinylpyrrolidone. By closely inspecting the growth process and the crystallographic analysis of as-synthesized products, conclusive evidence has been provided to show that the growth mechanism of such nanorod-bundles is imperfect oriented attachment. The anisotropic adsorption of polyvinylpyrrolidone at the different surfaces of Sb₂S₃ nanocrystals assists the one-dimensional preferential growth; it is just the misorientations that result in the nanorod-based superstructures. Moreover, the hydrothermal treatment time plays a crucial role, and can be used as the parameter to control the size and morphology of the bundles. This simple approach promises future large-scale controlled synthesis of various nanobody-based superstructures for many important applications in nanotechnology.