Abstract: Green walls (GW) can diminish building's surface temperature through shading, insulation, and evapotranspiration mechanisms. These can be analyzed by computer models that account for heat and mass transfer phenomena. However, most previous models were one-dimensional thermal simulations in which boundary conditions (BC), like convective moisture transport, were not or only partly considered. The present work proposes a more comprehensive way to predict GW's hygrothermal behavior by integrating a 3D multiphysics model that couples heat and moisture transport in Comsol Multiphysics®. The air cavity that usually separates the GW from the building was also considered. Heat sink terms were added to represent plants' transpiration and substrates' evaporation, considering the leaf area density (LAD) and substrate's water saturation (Sr). The model was validated against experiments where four green wall-test panels (GW-TPs) were evaluated in a climate chamber under steady-state conditions. This provides a much sounder approach for validation than what currently exists (r = 0.97; RMSE = 0.33 °C). The four GW-TPs decreased the masonry's surface temperature in the range of 0.89–1.14 °C (0.97 ± 0.11 SD °C). The average contribution of the evapotranspiration effect was 30%, whereas the contribution of the air cavity was 60.7 ± 0.09%. The temperature at the substrate's rear was reduced on average by 0.57 ± 0.15 SD °C. When solar radiation was considered as a BC, the GW-TPs decreased the building's surface temperature by 10 °C. Lastly, high values of LAD and Sr translated into increased temperature reduction values.