In this paper, a mathematical model dealing with a coupled heat, air, and moisture transfer in a building envelope was developed. Based on the three‐following driving potential: vapor pressure, dry air pressure, and temperature, an application on a hygrothermal behavior of a real wall was carried out for different climatic conditions. For this purpose, a characterization of the heat and moisture properties of the materials constituting the wall made with red brick and cement mortar was carried out in the laboratory. This was used to evaluate experimentally the input parameters of the model as a function of relative humidity. To validate the numerical model, an experimental platform was improved. The wall was set up in a double‐climatic chamber with different boundary conditions, and then the temperature and humidity evolutions were recorded using several sensors within the wall thickness. The results have highlighted a good agreement between numerical simulation results and experimental ones.