Metallosupramolecular π-amphiphiles are emerging as a new class of adaptive materials that combine the ability of π-conjugated systems to self-assemble in a “programmed” fashion and the versatile coordination geometry and well-known optical, electronic and magnetic properties of metal ions. In particular, their aqueous self-assembly is expected to yield a wide variety of supramolecular structures of unprecedented complexity through multiple noncovalent interactions. This approach provides access to smart materials with functionalities that can be controlled by environmental changes such as pH or the addition of metal ions. A wide range of applications can be envisaged in fields as diverse as catalysis, biomedicine or materials science.