Promotion of liquid‐crystalline behavior in oligothiophenes was achieved by M. Melucci and co‐workers (see p. 10046 ff.) by applying a new design‐strategy based on the insertion of a rigid inner core, such as dithienothiophene, benzothiadiazole, or carbazole, and hexyl chains as ends. Oligomers of different size and shape were synthesized by a highly efficient microwave‐assisted protocol. Most of the newly synthesized materials showed ordered smectic mesophases and maintained the smectic order by slow cooling to room temperature. Semiconducting behavior in field‐effect transistors from cast and vacuum‐evaporated films was demonstrated.