CuCl microcrystals with different morphologies such as tetrahedra, etched tetrahedra, tripod dendrites, and tetrapods were synthesized using CuCl2.2H(2)0 as the copper precursor in the mixed solvent of acetylacetone and ethylene glycol. The samples were characterized with X-ray diffraction, scanning electron microscopy, infrared spectroscopy, and transmission electron microscope. Cu(C5H7O2)(2) was identified as the key intermediate, and the morphology and structure of the CuCI microcrystals were highly dependent on the reaction time and temperature, as well as the volume of the solvents. The catalytic properties of these CuCI microcrystals were explored in the dimethyldichlorosilane synthesis via Rochow reaction. Compared to the commercial CuCl microparticles with irregular morphology and dense internal structure, the obtained CuCl microcrystals possessed regular morphology and different exposed crystal planes and showed much higher dimethyldichlorosilane selectivity and Si conversion via the Rochow reaction because of the enhanced formation of active CuxSi phase and gas transportation within the dendritic structure, demonstrating the significance of regular morphology of the copper-based catalysts in catalytic organosilane synthesis. (C) 2013 Elsevier Inc. All rights reserved.