The coordinated development of atmospheric pollution and socio-economic growth plays a core role in the sustainable development of cities and regions. The relationship between socio-economic growth and air pollution can be described using decoupling analysis. The seven key regions of China (168 cities), including Beijing–Tianjin–Hebei and its surrounding areas (BTHSR), the Yangtze River Delta region (YRDR), the Fen-Wei Plain (FWP), the Chengdu–Chongqing region (CCR), the urban agglomeration of the middle reaches of the Yangtze River (MLRYR), the Pearl River Delta region (PRDR), and other provincial capitals and municipalities with specialized plans (OPCCSP) were taken as targets to investigate the spatiotemporal evolution characteristics of AQI values and PM2.5 concentrations from 2014 to 2022. Then, the decoupling relationship between the AQI/PM2.5 and the socio-economic growth index (SEGI) in these key regions was deeply researched by the Tapio decoupling model. The main results were as follows: (1) Although the continuous improvement in air quality was observed in these seven key regions in China, the PM2.5 concentration in the BTHSR and FWP was still higher than 35 μg·m−3. The AQI showed a spatial pattern of high in the north and low in the south, and the distribution of PM2.5 in China was high in the east and low in the west. (2) The decoupling degree between air pollution and socio-economic growth was relatively high in the PRDR and YRDR. In contrast, the degree of decoupling was poor in the FWP and OPCCSP. The decoupling states were primarily influenced by industrial structure, energy consumption, and urbanization. (3) The decoupling of air pollution from socio-economic growth was in a strong decoupling state throughout the majority of the study period, achieving a comparatively ideal decoupling state in 2018. However, the overall decoupling states of the seven regions were not sustainable, and the decoupling stability was relatively poor. During the research period, the decoupling state between socio-economic growth and air pollution changed and was unstable.