<p>Achieving synergistic control of air pollution and carbon emissions (SCAPCE) is crucial for global sustainable development. This study leverages the exogenous shock from the Vertical Reform of the Management System of Environmental Protection Agencies (VRMS) to assess the efficacy of a centralized environmental regulatory system on SCAPCE. The findings indicate that the centralized environmental regulatory system has successfully achieved SCAPCE, with a decrease in annual inhalable particulate matter (PM₁₀) concentrations by 2.2945&#xa0;μg/m³ and a reduction in carbon dioxide (CO₂) emissions by 0.0124%. However, VRMS’s effectiveness is influenced by city characteristics. In midwestern regions, resource-based cities, and cities with extended oversight distances, VRMS’s impact is no longer statistically significant. Further analysis reveals that environmental administrative penalties act as an intermediary mechanism, while political attention enhances the SCAPCE effects of VRMS. A cost–benefit analysis shows that VRMS has led to a per capita gain of approximately 54 lifedays for the Chinese population. The aggregate economic value of these health benefits, based on willingness-to-pay, is approximately $1.53 billion, which translates to about $1.08 per person. This study offers a new insight from the foundational system of environmental regulation for achieving SCAPCE and deepens our understanding of environmental (de)centralization.</p> Graphical Abstract <p></p>