We designed and synthesized CuO/SnO2/Pd hollow microboxes, which was developed based on prepared Cu2O cubes coated Pd nanosheets, controlled oxidation of Cu2O/Pd, and etching of Cu2O/CuO/Pd by SnCl4 solution. The catalytic property of the Cu2O, Cu2O/SnO2, Cu2O/Pd/SnO2, Cu2O/Pd, Cu2O/CuO/Pd, CuO/SnO2/Pd, CuO, and commercial catalyst for dimethyldichlorosilane synthesis via the Rochow reaction was investigated. As compared to control samples and commercial catalyst, the prepared CuO/Pd/SnO2 hollow microboxes exhibited much higher silicon conversion (76.6%), which is related to the synergistic effect between CuO, Pd and SnO2, and to the distinct catalyst hollow structure which allows the efficient transportation of the reactant molecules to the active component.