This paper reports a facile solution route (water bath heating or hydrothermal heating) for synthesizing a few Sb-based self-assembly structures including bundles of nanowires, nanowire-flowers, long nanowires, bundles of flakes, nanobelts, hollow prisms. These obtained nanomaterials were characterized by XRD, FE-SEM, TEM, SAED, and HRTEM. It was found that the morphology, size and phase of self-assembly nanostructures were strongly dependent on reaction temperature, reaction time, pH value, and heating source. In particular, nanowire-flowers and hollow prisms of antimony oxide or oxychloride have not been reported previously. A possible mechanism based on stepwise nucleation and aggregation of nanowires or flakes was also proposed.