There is growing attention to the use of greenery in urban areas, in various forms and functions, as an instrument to reduce the impact of human activities on the urban environment. The aim of this study has been to investigate the use of green roofs as a strategy to reduce the urban heat island effect and to improve the thermal comfort of indoor and outdoor environments. The effects of the built-up environment, the presence of vegetation and green roofs, and the urban morphology of the city of Turin (Italy) have been assessed considering the land surface temperature distribution. This analysis has considered all the information recorded by the local weather stations and satellite images, and compares it with the geometrical and typological characteristics of the city in order to find correlations that confirm that greenery and vegetation improve the livability of an urban context. The results demonstrate that the land-surface temperature, and therefore the air temperature, tend to decrease as the green areas increase. This trend depends on the type of urban context. Based on the results of a green-roofs investigation of Turin, the existing and potential green roofs are respectively almost 300 (257,380 m2) and 15,450 (6,787,929 m2). Based on potential assessment, a strategy of priority was established according to the characteristics of building, to the presence of empty spaces, and to the identification of critical areas, in which the thermal comfort conditions are poor with low vegetation. This approach can be useful to help stakeholders, urban planners, and policy makers to effectively mitigate the urban heat island (UHI), improve the livability of the city, reduce greenhouse gas (GHG) emissions and gain thermal comfort conditions, and to identify policies and incentives to promote green roofs.