Abstract Various phosphazenylcyclophosphazenes N3P3Xn(N = PA3)6-n with X = Cl, F, A = Me, Ph, NMe2, OEt, OPri, OButn and n = 1-3 were obtained by desilylation methods. Chemical and spectroscopical properties dependent on the substituents are discussed. Isomers of di-and tri-substituted compounds were isolated and their structures elucidated by NMR spectroscopy.