A novel rational synthetic pathway-the "functionalization of para-nitroaniline" (FpNA)-provides substituted hexaarylbenzenes (HABs) with uncommon symmetries that bear up to five different substituents, fully avoiding regioisomeric product distributions during the reactions. 4-Nitroaniline is functionalized by a cascade of electrophilic halogenations, Sandmeyer brominations, and Suzuki cross-coupling reactions, leading to 26 substitution geometries, of which 18 structures are not available by the current established techniques. Furthermore, we demonstrate that this method is applicable to the bulk production of such systems on a multigram scale. Regarding optoelectronic properties, we demonstrate how highly functionalized HABs can show strong luminescent behavior, making these molecules very attractive to organic electronic devices.