Hexaarylbenzenes (HABs) have been attracting a great deal of research interest derived from their propeller-shaped geometry. Well-designed multi-substituted HABs have unique utilities, such as organic electronics and scaffolds for supramolecular assembly. However synthetic methods for multi-substituted HABs are limited. In this mini review, I describe recent advances in rational synthesis of HAB with 5 or 6 different aryl groups.