After the reform and opening up, China’s economy has developed rapidly. However, environmental problems have gradually emerged, the top of which is air pollution. We have used the following methods: In view of the shortcomings of the current spatio-temporal evolution analysis of the Air Quality Index (AQI) that is not detailed to the county level and the lack of analysis of its underlying causes, this study collects the AQI of all counties in China from 2014 to 2021, and uses spatial autocorrelation and other analysis methods to deeply analyze the spatio-temporal evolution characteristic. Based on the provincial panel data, the spatial econometric model is used to explore its influencing factors and spillover effects. The research results show that: (1) From 2014 to 2021, the AQI of all counties in China showed obvious spatial agglomeration characteristics, and counties in central and western Xinjiang, as well as Beijing, Tianjin, and Hebei, were high-value agglomeration areas; (2) the change trend of the AQI value also has obvious spatial autocorrelation, and generally presents a downward trend. However, the AQI value in a small number of regions, such as Xinjiang, shows a slow decline or even a reverse rise; (3) there are some of the main factors affecting AQI, such as GDP per capita, percentage of forest cover, total emissions of SO2, and these factors have different impacts on different regions. In addition, the increase of GDP per capita, the reduction of industrialization level, and the increase of forest coverage will significantly improve the air quality of other surrounding provinces. An in-depth analysis of the spatio-temporal evolution, influencing factors, and spillover effects of AQI in China is conducive to formulating countermeasures to improve air quality according to local conditions and promoting regional sustainable development.