The synthesis of polyhetarylenes containing exclusively s-tetrazine and another nitrogen heterocycle (pyridine or s-triazine) is described. The key step involved the polymerization of a suitable di-or triamidrazone, leading to a linear or hyperbranched dihydrotetrazine-based assembly, respectively. The triazinylenetetrazinylene material stands as one of the most nitrogenated polymers ever described.
