Thienoacenes and furoacenes are among the most frequent molecular units found in organic materials. The efficient synthesis of morphologically different heteroacenes and the rapid determination of their solid-state and electronic properties are still challenging tasks, which slow down progress in the development of new materials. Herein, we report a flexible and efficient synthesis of unprecedented heterotetracenes based on a platinum- and gold- catalyzed cyclization-alkynylation domino process using EthynylBenziodoXole (EBX) hypervalent iodine reagents as key step. The proof-of-principle in silico estimation of the synthesized tetracenes' charge transport properties reveals their strong dependence on both the position and nature of the heteroatoms in the ring system. A broad range of mobilities is predicted, with some compounds displaying performance potentially comparable to that of state-of-the art electronic organic materials.