Four N‐acenoacenes were synthesized and analyzed for their optoelectronic properties and solid‐state packings. Two of the regioisomeric acridinoacridines are TIPS‐ethynylated, whereas the other pair are Boc‐ and triflate substituted derivatives. The two TIPS‐ethynyldiazaacenoacenes were processed into organic thin‐film transistors with saturation hole mobilities reaching 2.9×10−2 cm2(Vs)−1.