Air quality degradation presents a significant public health challenge, particularly in rapidly urbanizing regions where changes in land use/land cover (LULC) can dramatically influence pollution levels. This study investigates the association between LULC changes and air pollution (AP) in the five fastest-growing cities of Bangladesh from 1998 to 2021. Leveraging satellite data from Landsat and Sentinel-5P, the analysis reveals a substantial increase in urban areas and sparse vegetation, with declines in dense vegetation and water bodies over this period. Urban expansion was most pronounced in Sylhet (22-254%), while Khulna experienced the largest increase in sparse vegetation (2-124%). Dense vegetation loss was highest in Dhaka (20-77%) and water bodies (9-59%) over this period. Concentrations of six major air pollutants (APTs) - aerosol index, CO, HCHO, NO2, O3, and SO2 - were quantified, showing alarmingly high levels in densely populated industrial and commercial zones. Pearson's correlation indicates strong positive associations between APTs and urban land indices (R > 0.8), while negative correlations exist with vegetation indices. Geographically weighted regression modeling identifies city centers with dense urban built-up as pollution hotspots, where APTs exhibited stronger impacts on land cover changes (R2 > 0.8) compared to other land classes. The highest daily emissions were observed for O3 (1031 tons) and CO (356 tons) at Chittagong in 2021. In contrast, areas with substantial green cover displayed weaker pollutant-land cover associations. These findings underscore how unplanned urbanization drives AP by replacing natural land cover with emission sources, providing crucial insights to guide sustainable urban planning strategies integrating pollution mitigation and environmental resilience.