In this work, we report a simple and inexpensive approach to synthesize effective multicomponent Cu-Cu2O-CuO catalysts for the Rochow process from industrial waste contact masses (WCMs). WCMs from the organosilane industry were treated with acid followed by reduction with metallic iron powder. The obtained copper powder was then subjected to controlled oxidation in air at different temperatures, followed by ball milling. The orthogonal array approach was applied to optimize this process, and the stirring speed and pH were found to significantly affect the leaching ratio and copper yield, respectively. When used for the Rochow process, the optimized ternary Cu-Cu2O-CuO catalyst greatly enhanced the dimethyldichlorosilane selectivity and Si conversion compared with Cu-Cu2O-CuO catalysts prepared without ball milling, bare Cu catalysts, and Cu-Cu2O-CuO catalysts with different compositions. This could be attributed to their small particle size and the strong synergistic effect among the multiple components in the catalyst with the optimized composition. (C) 2017 Chinese Society of Particuology and Institute of Process Engineering, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.