Abstract: | A series of novel imide‐functionalized ladder‐type heteroarenes with well‐defined structure and controllable conjugation lengths were synthesized and characterized. The synthetic route shows remarkable efficacy for constructing the electron‐deficient ladder backbones. π‐Conjugation extension leads to narrowed band gaps with enhanced electron affinities. The ladder arenes are incorporated into organic thin‐film transistors, and show encouraging electron mobilities of 0.013–0.045 cm2 V−1 s−1. The heteroarenes reported here provide a remarkable platform for fundamental physicochemical studies and materials innovation in organic electronics. |