Considerable efforts have been devoted to achieving stable acene derivatives for electronic applications; however, the instability is still a major issue for such derivatives. To achieve higher stability with minimum structural change, CC units in the acenes were replaced with isoelectronic BN units to produce a novel BN‐embedded tetrabenzopentacene (BNTBP). BNTBP, with a planar structure, is highly stable to air, moisture, light, and heat. Compared with its carbon analogue tetrabenzopentacene (TBP), BN embedment lowered the highest occupied molecular orbital (HOMO) energy level of BNTBP, changed the orbital distribution, and decreased the HOMO orbital coefficients at the central carbon atoms, which stabilize BNTBP molecules upon exposure to oxygen and sunlight. The single‐crystal microribbons of BNTBP exhibited good performance in field‐effect transistors (FETs). The high stability and good mobility of BNTBP indicates that BN incorporation is an effective approach to afford stable large‐sized acenes with desired properties.

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Introducing BN units into polycyclic aromatic hydrocarbons expands the chemical space of conjugated materials with novel properties.H owever,i ti sc hallenging to achieve accurate synthesis of BN-PAHs with specific BN positions and orientations.H ere,t hree new parent B 2 N 2perylenes with different BN orientations are synthesized with BN-naphthalene as the building block, providing systematic insight into the effects of BN incorporation with different orientations on the structure,(anti)aromaticity,crystal packing and photophysical properties.T he intermolecular dipole-dipole interaction shortens the p-p stacking distance.The crystal structure,(anti)aromaticity,and photophysical properties vary with the changeo fB No rientation. The revealed BN doping effects may provide ag uideline for the synthesis of BN-PAHs with specific stackings tructures,a nd the synthetic strategy employed here can be extended towardt he synthesis of larger BN-embedded PAHs with adjustable BN patterns.