An insoluble disclike building block hexa(4-iodophenyl)-peri-hexabenzocoronene (see picture) was synthesized in an efficient way, and subsequent functionalization led to a series of soluble, star-type hexabenzocoronenes (HBCs), all showing remarkable self-assembly behavior: 1) highly ordered liquid-crystalline materials, 2) dendronized HBCs, and 3) triarylamine-substituted HBCs.