Since the serendipitous event that led to the first synthesis of a molecule by the hands of Man in 1826, the creation of molecular matter depended for 150 years on linking together molecules from other molecular building blocks with the help of strong covalent bonds. The advent of supramolecular chemistry in the last decades of the 20th century has provided chemists with a wealth of new possibilities to synthesize molecular structures and materials that are held together by relatively weak, non-covalent interactions, such as hydrogen bonding, π–π stacking, electrostatic and van der Waals interactions. Using nature as a source of inspiration, the creation of even more complex supramolecular architectures has recently become possible by applying the concept of hierarchical self-assembly, i.e. the non-covalent organization of molecules and macromolecules which takes places over distinct multiple levels, in which the assembly processes gradually decrease in strength. This review will focus on some recent discoveries in the field of spontaneous hierarchical organization of synthetic amphiphiles, disk-like molecules and concave building blocks into well-defined nano-sized assemblies.