Gas phase methylation of methyltrichlorosilane with methyl chloride to high-valued dimethyldichlorosilane was carried out by using metallic aluminum as a chlorine acceptor in the co-presence of activated carbon, tin, and zinc. The addition of activated carbon in metallic aluminum significantly enhanced the methylation of methyltrichlorosilane, and dimethyldichlorosilane was dominantly produced. Activated carbon played a catalyst role in the methylation reaction. When active metals, such as tin and zinc, were added in the mixture of aluminum and activated carbon, the active metals and activated carbon synergistically catalyzed the methylation of methyltrichlorosilane with methyl chloride toward the formation of dimethyldichlorosilane.