This study examines the relationship between spatiotemporal changes in ecological and natural map (ENM) grades and air pollution levels in the Yeongdong and Yeongseo regions of Gangwon Province, South Korea. In addition, it focuses on how changes in ENM areas associated with urbanization and industrialization relate to regional air quality variations while considering the two regions’ geographic, topographic, meteorological, and climatic characteristics. Using the Taebaek Mountain Range as the geological boundary, the study area was divided into seven districts in the Yeongdong region and 11 districts in the Yeongseo region. Air pollutant concentration data from 2016~2023 were obtained from the urban air quality monitoring network (Air Korea) and analyzed through region-specific time-series analysis. ENM data were collected from the EcoBank platform, which provides time-series information on ENM grades by city or county over the same period. Spatial analysis showed that particulate matter (PM10 and PM2.5) concentrations were highest in Wonju in the Yeongseo region and were generally higher on the western side of the Taebaek Mountain Range, whereas ozone (O3) concentrations were higher in the Yeongdong region. Correlation analysis revealed negative relationships between Grade 1 ENM areas (high ecological value) and PM10, PM2.5, and NO2 concentrations, while positive correlations were observed for Grades 2 and 3. Ozone showed negative correlations across all ENM grades. These findings suggest that degradation of ecologically valuable areas due to land development may be closely associated with changes in regional air pollution levels. Future research should integrate additional environmental spatial datasets, such as the National Environmental Evaluation Map and Land Cover Maps from the Environmental Geographic Information Service (EGIS), to better understand the links between land-use change and air quality dynamics.