|In the quest for new cyanide-containing compounds of group 15 elements (pnictogens, especially arsenic, antimony, and bismuth), different possible synthetic access routes were investigated. Ternary anions of the general formula [Pn(CN)x]y‒ (Pn = Sb, Bi) were synthesized for the first time. Precisely, it was possible to isolate and characterize the anions [Sb(CN)5]2‒, [Bi(CN)5]2‒, [Bi(CN)6]3‒, and [Bi2(CN)11]5‒. Moreover, the hitherto unknown heterocyclic anion [AsC4N4]‒ was obtained. The reaction mechanism of the formation of [AsC4N4]‒ was studied in depth by quantum chemical calculations.