• U-Net achieved good performance in urban imperviousness density extraction from Sentinel-2 MSI data. • The hybrid approach using Random Forest and U-Net improved urban land cover classification accuracies. • The expansion of built-up areas resulted in high demand for provisioning and regulating ecosystem services. • The decrease in cropland and forest negatively affected ecosystem service supply. • The framework using Sentinel-2 MSI data and ES bundles is effective for urbanization monitoring and environmental impact. Rapid urbanization in developing countries often results in uncontrolled urban growth. In order to support sustainable urban development, reliable and up-to-date information on urban land cover changes and their environmental impact is needed. In this study, we aim at evaluating the potential of Sentinel-2 (S-2) Multispectral Instrument (MSI) data for urban land cover change monitoring and for analyzing resulting impacts on Ecosystem Services (ES) provision in Kigali, Rwanda. Land cover classification into eight distinct urban classes (84% overall accuracies, 0.8 Kappa) was performed on data from 2016 and 2021 using a hybrid approach combining Random Forest with a U-Net-based impervious surface segmentation that improved the delineation of urban areas. The bi-temporal land cover maps were then analyzed regarding landscape structure using Landscape Metrics (LM). Ecosystem service bundles were derived for both years and their changes were summarized. Service providing areas were further evaluated in terms of changes in spatial attributes and structure of patches. ES were aggregated into eight bundles and grouped into provisioning, regulating and supporting services. The bundles were further analyzed using a matrix spatially linking landscape units with service supply and demand budgets. The results illustrated that three urban development scenarios can be distinguished including infill through housing and infrastructures development in core urban areas, urban sprawl in fringe zones and the development of urban patches at distant locations intercepted by cropland. The results revealed that the changes in LM negatively affected ES supply mainly through a decrease in cropland and forest. The expansion of built-up areas resulted in a high demand for provisioning and regulating services, especially food and water provision, surface runoff mitigation and erosion control. This is the first study demonstrating that detailed monitoring of urbanization and resulting environmental impacts can be performed with open access S-2 MSI data in Sub-Saharan Africa. Moreover, the framework developed in this study has the potential to be transferred to other Sub-Saharan cities.