Hybrid molecules of π-conjugated carbon rings and BN-heterocyclic rings (h-CBNs) fused with each other have been a rare class of compounds due to the limited availability of their synthetic methods. Here we report the synthesis of new h-CBNs featuring a B4N4-heteropentalene core and polycyclic aromatic hydrocarbon wings. Using 1,2-azaborinine derivatives as a building block, we developed a rational synthetic protocol that allows the formation of a B4N4 ring in a stepwise manner, resulting in the fully fused ABA-type triblock molecules. Thus, three derivatives of 1 bearing naphthalene (1Naph), anthracene (1Anth), or phenanthrene (1Phen) wings fused with the B4N4 core were synthesized and characterized. Among them, 1Phen, which displays the highest triplet-state energy, was found to serve a host material for phosphorescent OLED devices, for which a maximum external quantum efficiency of 13.7 % was recorded. These findings may promote the synthesis of various types of h-CBNs aiming at new properties arising from the synergy of two different π-electronic systems.