Nongeminally substituted cyclic phosphazenes with various haloalkyl substituents were prepared using deprotonation-substitution reactions at the methyl groups of the cis isomers of nongeminally substituted cis-[Me(Ph)P = N](3), 2. Treatment of 2 with n-BuLi followed by reaction with organic halogenated reagents (RX = C2Cl6, BrC(O)CMe2Br, and ICH2COOEt) at low temperature afforded the various cyclic derivatives cis-[(XCH2)(Ph)PN](3) (3, X = Cl, 4, Br, and 5, 1). The mono- and dibromoalkyl derivatives, cis-[Ph-3(BrCH2)Me2P3N3], 6, and [Ph-3(BrCH2)(2)MeP3N3], 7, were also isolated along with 4 when the electrophile was dibromoethane. Reaction of cis-[Ph(BrCH2)PN](3), 4, with KSC(O)Me gave cis-[Ph(MeC(O)SCH2)PN](3), 8. The structures of all the cis cyclic phosphazenes were determined by NMR spectroscopy and X-ray diffraction. All retained the basketlike shape with the hydrophobic phenyl groups opposite the haloalkyl groups on the P3N3 ring. Thermal analysis of the new cyclic trimers indicates that ring-opening polymerization does not occur. The melting points and the thermal stabilities of haloalkyl cyclophosphazenes were higher than those of the parent compound 2.