Star‐shaped molecules are exciting non‐conventional mesogens in which more than two linear arms are symmertrically attached to a core building block via covalent or supramolecular bonds. The molecular structures comprise flexible, semi‐flexible and shape‐persistent scaffolds which may realize all kinds of mesophase topologies by nanosegregation. This requires different modes of self‐assembly depending on the mesogen structure, flexibility and void between the arms. Functionality can be incorporated by cores, arms and guest molecules generating multifunctional, highly organized complex materials for applications.