New side-armed ligands of lariat ether type 6-13 have been synthesized by the respective phenolysis and naphtholysis reactions of the parent isomeric ansa (2,4) and spiro (3,5) macrocyclosubstituted cyclophosphazenes of general formula N3P3CldO(CH&H~0),] (where n = 4,5), separated by column chromatograhy, and characterized by mass spectrometry and IH and 31P NMR spectroscopies. The synthesized side-armed ligands 6-13, as well as their respective functional chlorine-containing precursors 2-5, represent crown ethers with cyclophosphazene subunits and may thus be considered as diphosphaza[l6lcrown-6 or PNP16C6 (2,6,10), diphosphaza[19lcrown-7 or PNP19C7 (4,8,12), phospha[l4]crown-5 or P14C5 (3,7, 111, and phospha[l7lcrown-6 or P17C6 (5,9, 13). The one-pot method of synthesis developed for (aryloxy)-crowns 6-13, with the phenolysis (or naphtholysis) performed in situ immediately after completing the formation of the respective chlorine-containing macrocycles 2-5, made it possible to obtain high yields of the corresponding 16-and 19-membered ansa-PNP-cyclosubstituted side-armed diphosphaza-crowns PNP16C6 and PNP19C7 (6,8,10,12) and to isolate the stable 14-and 17-membered spiro-P derivatives P14C5 and P17C6 (7,9, 11,13), inaccessible by other synthetic routes. The diphosphaza-crowns thus obtained with B-naphthoxy substituents (10,121 offer promising prospects as new ligands of the P-pivot lariat ether type, capable of complexing both alkali and transition metal cations and of potential catalytic activity in phase and electron-transfer processes.