A series of N‐heteroheptacenes was synthesized from ortho‐thiophene‐substituted aryl azides using a Rh2II‐catalyzed C−H bond amination reaction to construct the thienoindole moieties. This reaction tolerated the presence of electron‐donating or withdrawing groups on the aryl azide without adversely affecting the yield of the amination reaction. The central thiophene ring was created from two thienoindole pieces through a Pd‐catalyzed Stille reaction to install the thioether followed by a Cu‐mediated Ullman reaction to trigger the cyclization. The photophysical and electrochemical properties of the resulting focused library of N‐heteroheptacenes revealed that the electronic nature is controlled by the arene substituent while single crystals grown reveal that the packing motif is influenced by the N‐substituent. Solution‐processed thin‐film OFET devices were fabricated with the N‐heteroheptacenes, and one exhibited a hole‐mobility of 0.02 cm2 V−1 s−1.