The easily rotatable peripheral aromatic rings around central benzene in hexaarylbenzene (HAB) derivatives create a very intriguing nonplanar, propeller-shaped geometry. Because of the very low susceptibility toward self-aggregation, HAB derivatives are much stronger candidates among various polyphenylenes/hetero-oligophenylenes when poor molecular cohesion and inefficient packing is required. However, the native properties of hexaphenylbenzene (HPB) can be varied by proper tailoring and substitution of the HAB core. The cohesion and packing in the structures of HAB aggregates induce effective structural variations so as to modify the fundamental features. Recently, HAB derivatives attracted a lot of research interest because of their significant role as liquid crystalline materials, organic light-emitting diodes, photochemical switches, redox materials, and molecular receptors. Herein, detailed attention is given to the pioneering work based on synthetic optimization of different HAB cores, elaborated study of their crystal engineering, various interesting applications of HAB derivatives, and future possibilities and capabilities of this still underexplored scaffold.