N-directed 2-fold bromoboration reactions of diynes with BBr3 have been developed, allowing the access to novel internally BN-doped polycyclic aromatic hydrocarbons from readily available precursors under mild conditions. Computational investigations identified three potential reaction mechanisms, each involving either BBr3 or [BBr4]-, with low activation barriers (ΔG‡ < 16 kcal/mol) for all pathways. The resulting brominated products can be further functionalized through various cross-coupling protocols, enabling the synthesis of highly luminescent emitters with quantum yield exceeding 90.