Most air pollution research has focused on assessing the urban landscape effects of pollutants in megacities, little is known about their associations in small- to mid-sized cities. Considering that the biggest urban growth is projected to occur in these smaller-scale cities, this empirical study identifies the key urban form determinants of decadal-long fine particulate matter (PM2.5) trends in all 626 Chinese cities at the county level and above. As the first study of its kind, this study comprehensively examines the urban form effects on air quality in cities of different population sizes, at different development levels, and in different spatial-autocorrelation positions. Results demonstrate that the urban form evolution has long-term effects on PM2.5 level, but the dominant factors shift over the urbanization stages: area metrics play a role in PM2.5 trends of small-sized cities at the early urban development stage, whereas aggregation metrics determine such trends mostly in mid-sized cities. For large cities exhibiting a higher degree of urbanization, the spatial connectedness of urban patches is positively associated with long-term PM2.5 level increases. We suggest that, depending on the city's developmental stage, different aspects of the urban form should be emphasized to achieve long-term clean air goals.