New heteroacenes, named coumarinacenes, have been designed, synthesized and characterized. They possess visible absorption and orange-red emission that are far beyond those of benzo[g]coumarins. They exhibit deep HOMO energy levels, and reveal excellent thermal, photochemical and air stabilities as compared to tetracene/pentacene. Their preliminary thin-film devices display encouraging transistor characteristics, moderate mobility and considerable environmental stability paving way into electronics. © 2020 Wiley-VCH GmbH