Supramolecular morphological transitions are of great importance in many processes in molecular biology. The Golgi apparatus bilayer, for instance, constantly transforms into cargo vesicles mediated by coaggregation with protein coats, but also proteins fold and unfold by coaggregation with chaperone proteins. In the latter case, chaperones selectively switch off the self-assembly of parts of the protein, thereby controlling their structure and function. Such a strategy can be of use for the development of smart materials, in which an external trigger induces a morphological transition, altering the macroscopic properties of the material. The use of coaggregation to induce morphological transitions has indeed been applied successfully to artificial systems, hence leading to the development of smart materials. The main strategy so far is to alter the packing parameter of a surfactant leading to morphological changes following the structure–shape concept. By this strategy, the transition of vesicles to hexagonal phases by the addition of trimethylbenzene, the conversions of spheres into rods into tubes by addition of ions as well as other additives have been induced. Other strategies to induce morphological changes have also been applied, for example, the use of twocomponent gel systems or photoisomerization of the building block. Although in all cases the mechanisms of these morphological transitions are well understood, the outcome can be hard to predict. Therefore, it remains a challenge to program the outcome of such transitions within the initial building block, which is necessary to use this approach for smart materials. Herein we demonstrate that morphological transitions can easily be programmed by separately addressing the complex aggregation behavior of a segmented self-assembling molecule, using small molecule chaperone analogues, that is, small molecules that selectively switch off self-assembly of another molecule through selective association. As a model system, we use a previously described multisegment amphiphile that consists of two covalently linked but orthogonally self-assembling building blocks, and which forms architectures characterized by each individual segment. Through the addition of a chaperone analogue we can selectively switch off the self-assembly of each of these segments individually, resulting in architectures of the other segment. Interestingly, not only the morphologies of the other segment are retained, but also its dynamics of self-assembly. By such an approach it is possible to design the morphological transitions within the multisegment amphiphile. The multisegment amphiphile (MA 3) is constructed of a gelator segment reminiscent of gelator 1 and a surfactant segment reminiscent of EO4C8 (surfactant 2), which assemble orthogonally (Figure 1a). We have previously shown that MA 3 in water assembles into architectures that display properties of both parental segments. The gelator segment