Urchin-like ZnO microspheres were successfully prepared by thermal decomposition of hydrozincite synthesized via homogeneous precipitation of zinc nitrate and urea in the presence of a nonionic surfactant polyethylene glycol. The synthesis conditions, such as reaction temperature and time, precursor concentration, and the amount of surfactant added, as well as the catalytic properties of urchin-like ZnO microspheres as promoters for a commercial copper catalyst in dimethyldichlorosilane synthesis were investigated. In addition, the formation mechanism of urchin-like microspheres from hydrozincite to ZnO was proposed. The ZnO samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, and N 2 adsorption. It was found that zinc nitrate concentration and the amount of surfactant are the key factors that lead to the formation of urchin-like ZnO microspheres. These ZnO samples had BET surface areas of 16-30 m 2 g -1 and an average diameter of 3-8 μm. Compared with commercial Zn microspheres and ZnO nanoparticles, urchin-like ZnO microspheres showed a better performance in dimethyldichlorosilane synthesis via the Rochow reaction due to their larger surface area, which created more interfacial contacts with the copper catalyst and active Cu 3Si species. The work is helpful for developing novel catalyst promoters and understanding the role of the promoter in the Rochow reaction.