Africa, as a major climate change hotspot, faces severe impacts, including extreme temperatures. Notably, urban areas are unequally affected by these impacts. The urban poor are particularly vulnerable to extreme temperatures, because of the environmental and physical characteristics of their neighbourhoods, and their limited resources to develop coping strategies. Limited knowledge exists of the spatial patterns of thermal inequalities within neighbourhoods. Our overall scientific objective is to explore the potential of Earth Observation (EO) to study how and why urban dwellers in the Global South (focusing on Africa) with different levels of deprivation are divergently exposed to varying temperatures and extreme heat, and to quantify the urban population exposed to such conditions. We make use of several state-of-the-art EO/AI models, and employ innovative in situ data collection methods together with local stakeholders through Citizen Science. We rely as far as possible on open or low-cost satellite imagery (e.g., Sentinel-1/2, Landsat, ECOSTRESS) for scalability and transferability, and we implement Machine Learning (ML) methods, including Deep Learning (DL). Results highlight significant local differences in thermal exposure, emphasizing the need to understand and communicate these spatial patterns to support the development of cost-effective adaptation strategies.