Novel Bi2S3 hierarchical nanostructures self-assembled by nanorods are successfully synthesized in mild benzyl alcohol system under hydrothermal conditions. The hierarchical nanostructures exhibit a flower-like shape. X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and selected area electron diffraction (SAED) were used to characterize the as-synthesized samples. Meanwhile, the effect of various experimental parameters including the concentration of reagents and reaction time on final product has been investigated. In our experiment. PVP plays an important role for the formation of the hierarchical nanostructures and the possible mechanism was proposed. In addition, Bi2S3 film prepared from the flower-like hierarchical nanostructures exhibits good hydrophobic properties, which may bring nontrivial functionalities and may have some promising applications in the future. (C) 2010 Elsevier Ltd. All rights reserved.