Flower-like nanostructures of Sb2 − xBixS3(x = 0.4, 1.0) were successfully prepared using both antimony diethyldithiocarbamate [Sb(DDTC)3] and bismuth diethyldithiocarbamate [Bi(DDTC)3] as precursors under solvothermal conditions at 180 °C. The prepared Sb2 − xBixS3 with flower-like 3D architectures were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDS), high-resolution transmission electron microscopy (HRTEM), and selected area electron diffraction (SAED). The flower-like architectures, with an average diameter of ~4 μm, were composed of single-crystalline nanorods with orthorhombic structures. The optical absorption properties of the Sb2 − xBixS3 nanostructures were investigated by UV–Visible spectroscopy, and the results indicate that the Sb2 − xBixS3 compounds are semiconducting with direct band gaps of 1.32 and 1.30 eV for x = 0.4 and 1.0, respectively. On the basis of the experimental results, a possible growth mechanism for the flower-like Sb2 − xBixS3 nanostructures is suggested.