Abstract: In view of the harmness and resource utilization of chlorosilane residues, the by-products are prepared into dimethyldichlorosilane with higher economic benefit through disproportionation reaction. The ZSM-5@γ-Al₂O₃ core-shell carrier was constructed by modifying the surface of ZSM-5 molecular sieve with Tianjing gum as the binder and γ-Al₂O₃ as the shell. NaAlCl₄ was loaded on the surface of ZSM-5@γ-Al₂O₃ core-shell carrier by high-temperature impregnation loading method. The effect of ZSM-5 molecular sieve with different Si/Al molar ratios on the disproportionation preparation of dimethyldichlorosilane, the effect of different NaAlCl₄ loading ratios and the impregnation time of AlCl₃ solution on the reaction of disproportionation preparation of dimethyldichlorosilane were investigated comprehensively, and the samples were characterized by XRD, SEM, SEM-EDS, BET and FTIR. The results show that the catalyst activity reach the optimum with 71.81% yield when the temperature is 200°C, the silica-alumina molar ratio is 50, the compound salt NaAlCl₄ ratio is 8wt%, and the AlCl₃ impregnation time is 3 h. The NaAlCl₄ compound salt loading on the surface of the ZSM-5@γ-Al₂O₃ core-shell catalyst shows the improved catalytic efficiency and enhanced performance instability compared with single catalytic component. Further redistribution chlorosilane by-products methyl trichlorosilane (M1) and trimethylchlorosilane (M3) synthesis can obtain high commercial value dimethyl dichlorosilane (M2), so as to realize the transformation of waste into treasure.