• Ambient wet bulb temperature limits cooling potential of a building component skin. • Daytime sol–air temperature limits heating potential of a building component skin. • Cooling and heating efficiency of the skin of a building component have been defined. • The efficiency of different skin systems are comparable in a unique value. The thermal evaluation of building components composed of a base wall with a solar passive skin solution, such as a vertical/roof greenery system, ventilated façade, reflective painting, etc., is usually performed as a whole. In this research, it has been proven that, independently of the base wall thermal inertia and insulation level, the temperature of the outermost surface layer of any building component during sunny hours is mainly dependent on the ambient air temperature and relative humidity, the incident global solar radiation and the building skin behaviour. The latter assumption has been proven on the south wall of a reference building simulated with TRNSYS. The south wall properties have been varied and the building has been subjected to different climates. The assumption’s validity has been checked for twelve south wall cases: a combination of 2 thermal transmittance, 2 thermal inertia and 3 climates. Each case has been simulated for a whole year. Based on this finding and the local ambient conditions for sunny hours, the hypothetical achievable maximum and minimum temperatures for the outermost surface layer have been defined. Then, based on the outermost surface temperature experimental measurements, the cooling and heating solar efficiencies valid for any skin solution have been defined. Furthermore, the developed methodology has been applied to a vertical living wall tested for a whole year under the accuracy and quality procedure of the PASLINK method. In this way, the cooling and heating solar efficiencies were experimentally determined for this skin solution for both, the hot cold seasons. The study has shown that the cooling efficiency during the hot season is 90.8%. As expected, even during sunny summer hours, the presence of water positively affects the performance of the façade, as it brings the base wall external surface temperature close to the ambient wet bulb temperature, therefore reducing the cooling load of the building. For the cold season, the cooling efficiency was similar, at 90.3%, which means a heating efficiency of 9.7%. Again, even for sunny winter hours, the values of the external surface temperature tend towards the ambient air wet bulb temperature, resulting in an increase in the heating demand. These experimental efficiency values allow the heating or cooling behaviour of different skin solutions to be comparable with a single number that is independent of the base wall composition. In addition, independently of the base wall composition, once the experimental efficiency value of a given skin solution is known, it allows (during sunny hours) the base wall outermost surface temperature to be calculated with precision. The latter makes it possible to increase the accuracy of the estimation of the heating and cooling demands of such methods as the degree-day method.