Abstract In recent years living walls have increasingly spread, thus becoming a diffuse architectural envelope cladding technology. Consequently, a more precise understanding of their thermal behavior and impact on the building energy balance are needed. One of the most important effects provided by the use of living walls is the shading of the building envelope, with clear benefits during the cooling period. Furthermore, many features characterize the thermal behavior of living walls, namely plant species, leaf area index (LAI), evapotranspiration, emissivity and air cavity type. All these particular characteristics have been accounted in the mathematical model developed in the frame of the presented research, whose aim is to provide a tool for the prediction of the thermal behavior of living walls. Two kinds of living walls, one with grass and closed air cavity and the other one with vertical garden and open air cavity were considered. The results achieved by means of the developed model show a good agreement with the measurements also supported by model efficiency indexes such as Nash–Sutcliffe efficiency index (NSEC). Values of around 0.7 were obtained for the NSEC index for both the investigated living walls.