Uniform 3D hierarchical flower-like CdWO₄ microstructures have been conveniently synthesized by using sodium cholate as a self-assembly facilitating agent at low temperature (35 °C). The flower-like CdWO₄ microspheres are composed of radiatively assembled monoclinic-crystalline CdWO₄ nanoplates with lengths of several hundred nanometers. It is noted that the introduction of sodium cholate can make the preparation of 3D CdWO₄ microspheres proceed at a much lower temperature than the hydrothermal treatment method. The morphological modulation of the products could be easily realized by controlling the reaction temperature, reaction time, dosage of sodium cholate, and concentration of cadmium-cholate precursors. Based on the characteristic results, a possible formation mechanism of 3D flower-like CdWO₄ microspheres was proposed.