China’s approach to air pollution control has been shown successful in East Asian countries and even elsewhere in the world. The analysis of the evolution and control of air pollution in China over the past 75 years can be used as a reference for developing countries suffering from air pollution resulting from urbanization. Based on the sorting and mining of relevant indicators, data and policy texts from the areas of population, economy, space and social urbanization, the findings suggest that the presence of air pollution and its changing forms indeed have complex interactive relationships with the process of urbanization. Specifically: (1) the feature of air pollution has changed from “single pollutant and pollution source to multiple pollutants and pollution source, local pollution to regional pollution, light pollution to heavy compound pollution” as a result of urbanization, the emphasizing of construction and the neglect of governance, the emphasizing of economics and the neglect of ecology, and the emphasizing of immediate interests over long-term interests; (2) the interactive relationship between air pollution and urbanization has also gone through three stages from being irrelevant each other to “urbanization determines air pollution” and then “air pollution restricts urbanization”; (3) this has forced air pollution control to shift from the traditional “treating symptoms” to “high-quality urbanization”, thus promoting air pollution and urbanization to move “from confrontation to unification”. Therefore, air pollution control is not a simple technical issue; one of the keys lies in exploring how to adjust the urbanization model, so as to achieve the “win–win” of urbanization and air pollution control.

Over the past 70 years since the founding of the People’s Republic of China, urban development has achieved remarkable progress but also encountered severe atmospheric pollution, which has become a significant obstacle to high-quality urban development. Understanding the interaction mechanisms between urban development and atmospheric pollution is thus crucial for promoting sustainable urban construction. This paper explores these mechanisms by analyzing the interplay between urban population, industry, space, social development, and pollution through a theoretical framework. Using a simultaneous equations model and the Three-Stage Least Squares (3SLS) method, it examines these relationships and further investigates threshold effects. The findings reveal a nonlinear relationship with significant thresholds: (1) High levels of PM_2.5, population size, and industrial agglomeration can shift from exacerbating pollution to enabling governance, though excessive thresholds reverse this trend. (2) PM_2.5 mediates the impact of spatial sprawl, environmental regulation, and population dynamics, oscillating between governance and pollution effects. (3) Industrial agglomeration and spatial sprawl show variable impacts on pollution mitigation depending on pollution intensity and urban thresholds. These findings provide critical insights into the intricate dynamics between urban development and atmospheric pollution, emphasizing the importance of adopting differentiated strategies based on specific urban thresholds. Ultimately, this research contributes to the broader goal of harmonizing economic growth, social development, and environmental sustainability in urban areas, serving as a valuable reference for cities worldwide facing similar challenges.