Green roofs are artificial ecosystems that provide a nature-based solution to environmental problems such as climate change and the urban heat island effect by absorbing solar radiation and helping to alleviate urban environmental, economic, and social problems. Green roofs offer many benefits in terms of heat and water conservation as well as in terms of energy costs. This work proposes the design of an extensive and environmentally sustainable green roof for the Faculty of Engineering building in Bilbao. The green roof will be made from the composting of food waste generated in the building’s own canteen. Therefore, the main objective of this study is to calculate the solar efficiency of a sustainable green roof, evaluate its thermal performance, and quantify the impact that its implementation would have on energy consumption and the thermal comfort of its users. The results obtained confirm that an environmentally sustainable green roof has a positive effect on summer energy consumption and that this effect is much greater when there is water on the roof, as shown by the difference in energy savings between the dry (−53.7%) and wet (−84.2%) scenarios. The data show that in winter the differences between a green roof and a non-vegetated roof are not significant. In this case, the estimated energy consumption penalty (0.015 kWh/m2) would be 10% of the summer gain.