The study focuses on the multi-layer envelope systems (understood as multiple-skin façades), whereby the combination of the planar surfaces generates equipment with greenhouse effect, chimney effect and natural ventilation (in the form of double-skin façades): then, performance is concretized on the basis of treatment practices (thermal, chemical and surface), layering and coating (acting on the transmission of visible, solar and thermal radiation, especially with the reference to the infrared spectral field) and deposition on the perimeter enclosures. With respect to the enclosure elements, the application focuses on the physic of the glazed, combined and multi-layered surfaces, which experimental research tends to transform into dense, intelligent systems interfaces: the main materials constituting the external surfaces are composed according to their processes of change from stable entities to designable entities according to a particular performance program. In this case, the application of the materials of the envelope, in the form of projectable entities, is structured with respect to the outcomes of the solutions in which functions tend to become complex (in a controlled and managed manner) and articulated with each other, realizing multiple performances through the correlation of different agents and layers. The advanced envelope systems are specified in the constitution of integrated functional components with the objective of receiving, guiding and selecting the environmental loads to realize calibrated ergonomic conditions in the built spaces. For this, the systems are endowed with engineering performances (such as multiple environmental performances), are articulated in the form of environmentally responsive walls (capable of actively responding to environmental stresses through perceptual and organic contact with the climatic conditions) and as engineered walls (such as equipment that can be operated by mechanical devices), aimed at regulating the transmission of heat, light and natural ventilation, along with the attenuation of wind and acoustic loads.