The first examples of metalated stabilized diaminophosphonium diazaylides 7 have been synthesized in good yields from acylazides by two different synthetic pathways involving either an original and direct Staudinger reaction with the sodium phosphide (diazaylides 7′) or a more classical Staudinger reaction with diphenylphosphine and a subsequent deprotonation (diazaylides 7′). Additionally, the related new diaminophosphonium monoazaylides 6 and diaminophosphonium salts 5 have also been synthesized.