In this work, we prepared azoiodaziniums as a new class of six-membered heterocyclic iodonium salts with a wide range of substituents. Derivatizations of the reactive iodonium center allow the formation of new heterocyclic compounds based on azoiodazinium as reactive intermediates. Most interestingly, functionalization of the heteroarene salts was achieved without an undesired attack of the delicate C-I-bond at the hypervalent iodine center.