The population experiencing high temperatures in cities is rising due to anthropogenic climate change, settlement expansion, and population growth. Yet, efficient tools to evaluate potential intervention strategies to reduce population exposure to Land Surface Temperature (LST) extremes are still lacking. Here, we implement a spatial regression model based on remote sensing data that is able to assess the population exposure to LST extremes in urban environments across 200 cities based on surface properties like vegetation cover and distance to water bodies. We define exposure as the number of days per year where LST exceeds a given threshold multiplied by the total urban population exposed, in person ⋅ day. Our findings reveal that urban vegetation plays a considerable role in decreasing the exposure of the urban population to LST extremes. We show that targeting high-exposure areas reduces vegetation needed for the same decrease in exposure compared to uniform treatment.