We report the preparation of Cu 2O microparticles with different shapes, by simple hydrolyzation and reduction of copper acetate with glucose in a mixture of water-ethanol solvent. The effect of the synthesis conditions on the shape of the Cu 2O microparticles and their catalytic properties in the Rochow reaction were investigated. The samples were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, temperature-programmed reduction, and thermogravimetric analysis. Cu 2O microparticles with different shapes, such as hexahedron, ananas-like, sphere-like, and star-like shapes, with particle sizes of 2-4 μm, were obtained by tuning the volume ratio of water:ethanol. The hexahedron Cu 2O microparticles were found to exhibit the best catalytic performance for the synthesis of dimethyldichlorosilane via the Rochow reaction. This work should be helpful in the design and development of novel copper catalysts for organosilane synthesis and understanding their catalytic roles.