A direct and simple surfactant- and template-free route has been developed for the controlled synthesis of Sb2O3 belt-like microstructures. By adjusting the reactant ratio between SbCl3 and urea under solvothermal reaction conditions, broom-like belts and rods of Sb2O3 have been successfully prepared. X-ray powder diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), and X-ray photoelectron spectroscopy (XPS) has been used to characterize the phases and morphologies of the as-prepared products. A possible formation mechanism is also discussed.