The construction of supramolecular architectures by the spontaneous self-assembly of molecules is currently a subject of great interest in areas that range from chemistry and biology to materials science.[1] Of particular interest is the design of externally addressable molecules that contain selfassembly elements, as these can give rise to so-called “smart materials”.[2] Such addressable molecules could include among others, photochromics, which can be used to bring about light-induced changes in the self-assembly [3, 4] or environment-sensitive luminophores, which can provide valuable insight into the nature of the molecular aggregation within such assemblies.[5] Herein, we present a novel class of donor–acceptor-substituted amphiphilic butadienes (Scheme 1) capable of undergoing spontaneous concentration-dependent hierarchical self-assembly from vesicles to gels. The self-assembly process was associated with unique changes in the fluorescence of the system. Moreover, the presence of a photoisomerizable chromophore makes these