Advanced materials are often based on smart molecular self-assemblies that either respond to external stimuli or have hierarchical structures. Approaches to this goal usually stem from complicated molecular design and difficult organic synthesis. In this invited feature article, we demonstrate that desired molecular self-assemblies can be made conveniently by introducing simple functional molecules into amphiphilic systems. We show that upon introducing specific small molecules which serve as responders, modulators, or even building blocks, smart supramolecular architectures can be achieved which avoid complicated organic synthesis. We expect that this could be a general and economical way to produce advanced materials in the near future.