Constitutional self-instructed membranes were developed and used for mimicking the adaptive structural functionality of natural ion-channel systems. These membranes are based on dynamic hybrid materials in which the functional self-organized macrocycles are reversibly connected with the inorganic silica through hydrophobic non-covalent interactions. Supramolecular columnar ion-channel architectures confined within scaffolding hydrophobic silica mesopores can be structurally determined and morphologically tuned by alkali salts templating. From the conceptual point of view these membranes express a synergistic adaptive behavior: the addition of the fittest alkali ion drives a constitutional evolution of the membrane toward the selection and amplification of the specific transporting superstructures within the membrane in the presence of the cation that promoted its generation in the first place. This is the nice example of dynamic self-instructed (“trained”) membranes where a solute induces the upregulation (prepare itself) of its own selective membrane. 1. A. Cazacu, Y.M. Legrand, A. Pasc, G. Nasr, A. van der Lee, E. Mahon, M. Barboiu, Proc. Natl. Acad. Sci., 2009, 106(20), 8117-8122. 2. M. Barboiu, Chem. Commun. 2010, 46, 7466-7476.S. Mihai, J. Dauthier, Y. Le Duc, A. El Mansouri, A. Mehdi, M. Barboiu, Eur. J. Inorg. Chem. 2012, DOI: 10.1002/ejic.20120075 3. M. Barboiu, A. Cazacu, S. Mihai, Y.-M. Legrand, G. Nasr, Y. Le Duc, E. Petit, A. van der Lee, Dynamic constitutional hybrid materials-toward adaptive self-organized devices, Microp. Mesop. Mat. 2011, 140, 51-57.