Many studies have shown that fine particulate matter can cause health problems. Thus, effectively controlling fine particulate matter concentration is an important issue around the world. The Taiwan Environmental Protection Administration (TWEPA) divides Taiwan into seven air quality zones based on counties and cities for managing air quality and analyzing pollution transmission. However, this artificial division by administrative areas relatively poorly match natural conditions and topographical and geographic factors and hence poorly represent air quality characteristics. This study proposes an air quality sensitive map analysis framework, which uses hierarchical agglomerative clustering with empirical orthogonal function and analysis of variance methods, to provide more detailed, reasonable, and township-level air quality zones incorporating the different spatial-temporal characteristics over the region. The risk concept is introduced to evaluate PM2.5 risk sensitivity for each administrative district, combining three aspects: hazard (PM2.5 exceedance probability), exposure (population density of sensitive groups), and vulnerability (average wind speed). Considering air quality spatial-temporal characteristics, Taiwan can be optimally divided into 14 air quality zones. PM2.5 risk is highest for western inland towns than western coastal towns, with eastern regions exhibiting least risk. Adopting the proposed air quality zones and clarifying high risk areas allows PM2.5 causes to be identified for different air quality zones. This allows a targeted control strategy for high risk areas to effectively improve domestic air quality. The proposed model also provides powerful reference for environmental management and environmental impact assessment for future construction and development.