Abstract For the first time phosphomacrocyclic systems were synthesized based on 2, 2′- dihydroxy-1, 1′-dinaphthylmethane, other aromatic diols, and phosphorous hexaethyltriamide. Spontaneous transformation of the obtained macrocycles into the more stable 1, 3, 2-dioxaphosphacyn and cyclobisamidophosphite was established.