Owing to their “dual” affinity, amphiphiles self-assemble in water to form different kinds of nanoscale multimolecular assemblies ranging from simple micelles and vesicles to highly organized fibers, helices and tubes. In this tutorial review the aggregates formed in water by head/tail amphiphiles are revisited and discussed from the point of view of supramolecular chemistry with a focus on their structure and recognition abilities. Their applications in materials chemistry, as soft templates for inorganic nanostructures, as well as in biological and medicinal chemistry are also illustrated. Special attention is paid to highlight intriguing aspects, for example the control of morphology and chirality, their modulation by experimental parameters and chiral symmetry breaking.