The reactions of N2O2-donor-type aminopodands 1-3 with trimer N3P3Cl6 led to the novel spirocyclic phosphazene derivatives 4-10 (Scheme). Compounds 4-7 and 8-10 are the first examples of the substituted spiro-ansa-spiro and spiro-bino-spiro phosphazene derivatives, respectively. The pyrrolidinyl-substituted phosphazene derivatives 7 and 10 were synthesized from 5 and 9, respectively, with an excess of pyrrolidine. ne reaction of aminopodand 3 (R=(CH2)(4)) with N3P3Cl6 in dry THF afforded only spiro-ansa-spiro phosphazene 6. The molecular structure of compound 9 was determined by X-ray diffraction: it shows the novel spiro-bino-spiro phosphazene architecture.