The reactions of fluorophosphazenes, endo ansa FcCH(2)P(S)(CH2O)(2)[P(F)N](2)(F2PN) (1) (Fc = ferrocenyl) and spiro [RCH2P(S)(CH2O)(2)PN](F2PN)(2) (R = Fc (2), C6H5 (3)], with dilithiated diols have been explored. The study resulted in the formation of the first examples of ansa-spiro substituted fluorinated cyclophosphazenes as well as a bisansa substituted fluorophosphazene. The bisansa compound {1,3-[FcCH(2)P(S)(CH2O)(2)]}{5-[CH2(CH2O)(2)]}N3P3F2 (4) was found to be nongeminaly substituted with both the ansa rings in cis configuration, which is in stark contrast to the observations on cyclic chlorophosphazenes where geminal bisansa formation has been observed. The ansaspiro compounds (5-7) underwent the ansa to spiro transformation leading to dispiro compounds in the presence of catalytic amounts of CsF at room temperature. Two of the ansa-spiro compounds, endo-{3,5-[FcCH(2)P(S)(CH2O)(2)]}{1,1-[CH2(CH2O)(2)]}N3P3F2 (5) and endo, {3,5-[FcCH(2)P(S)(CH2O)(2)]}{1,1,-[FcCH(2)P(S)(CH2O)(2)]}N3P3F2 (6), were structurally characterized, and the crystal structures indicate boat-chair conformation as well as crown conformation for the eight-membered ansa rings. Weak C-(HF)-F-...-P interactions observed in the crystal structures of the ansa-spiro substituted fluorophosphazene derivatives have been analyzed and compared with C-(HF)-F-...-P interactions of other fluorinated phosphazenes and thionyl phosphazenes.