Metal-mediated reactions of amidoximes with nitrile ligands are discussed and recent works of the author are considered to allow the reader to better understand the amidoxime reactivity patterns. General routes of activation of amidoxime and nitrile substrates in the studied reactions are considered. Reactions employing amidoximes as HO- and HN-nucleophiles, as well as reactions of amidoximes with nitrile ligands leading to heterocyclic systems are discussed.