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The Rochow‐Müller process, an old process that has been known for more than seventy years, is for the direct synthesis of methylchlorosilane. However, due to its unique economic efficiency, it is still extremely important in silicone industry, e. g., about 90 % of starting materials for producing silicones are obtained by this route. Although significant progress has been made in exploring high‐efficient catalysts and understanding its mechanism, a quantitative description of this reaction is still far‐fetched due to its high complexity. In addition, sustainable use and recycling of by‐products and waste solid have become imperative nowadays due to the increasing demands for atom economy and environmental protection. This paper provides a comprehensive overview and insights into Rochow‐Müller process from its catalysis to sustainable issues, including the catalyst development and reaction mechanism investigation, waste reutilization and their derived products. In addition, several emerging novel processes originated from Rochow‐Müller process are summarized. Lastly, challenges and perspectives with respect to this reaction are discussed. We hope this work has accurately reflected and recorded the transition of Rochow‐Müller process to modern molecular catalysis, and can promote a much more sustainable silicone industry.

Single-atom catalysts are of great interest because they can maximize the atom-utilization efficiency and generate unique catalytic properties; however, much attention has been paid to single-site active components, rarely to catalyst promoters. Promoters can significantly affect the activity and selectivity of a catalyst, even at their low concentrations in catalysts. In this work, we designed and synthesized CuO catalysts with atomically dispersed co-promoters of Sn and Zn. When used as the catalyst in the Rochow reaction for the synthesis of dimethyldichlorosilane, this catalyst exhibited much-enhanced activity, selectivity and stability compared with the conventional CuO catalysts with promoters in the form of nanoparticles. Density functional theory calculations demonstrate that single-atomic Sn substitution in the CuO surface can enrich surface Cu vacancies and promote dispersion of Zn to its atomic levels. Sn and Zn single sites as the co-promoters cooperatively generate electronic interaction with the CuO support, which further facilitates the adsorption of the reactant molecules on the surface, thereby leading to the superior catalytic performance.