In the present investigation, it is observed that condensation reactions of hexachlorocyclotriphosphazene, N3P3Cl6 (HCCP, trimer) and four different diamines (1-4) yielded tetrachloromono (5, 7 and 8) and bisferrocenyl (6) spirocyclotriphosphazenes. Reactions of 5, 7 and 8 with two equimolar amounts of 1-aza-15-crown-5 ether (L) produced new monoferrocenylspirocyclotriphosphazabis(crown ethers) (9, 10 and 12) in THF, respectively. The only monoferrocenylspirocyclotriphosphazatris(crown ether) (13) was obtained from the reaction of 8 with three equimolar amounts of L. However, reactions of 7 and 8 with four equimolar amounts of L resulted in the formation of monoferrocenylspirocyclotriphosphaza-tetrakis(crown ethers) 11 and 14. In addition, the complexation reactions of ditopic phosphaza-crown ethers (9, 10 and 11) with NaClO4 yielded novel mononuclear sandwich-type sodium complexes (9a, 10a and 11a). Tri-and tetranuclear complexes (13a and 14a) were obtained as a result of the complexation reactions of tri-and tetratopic phosphaza-crown ethers (13 and 14) with NaClO4. Characterizations of phosphaza-crown ethers and complexes were performed using elemental analysis, mass spectrometry, FTIR, and H-1, C-13 and P-31 NMR techniques. Ditopic phosphazenes (9, 10 and 12) and complexes (9a, 10a and 11a) have a stereogenic P center. While the tritopic ligand (13) and complex (13a) have two stereogenic P centers. They are expected to be in racemic mixtures. In addition, crystal structures of phosphazenes 6 and 9 were elucidated using X-ray crystallography. The absolute configurations of the enantiomers of 9 were determined as R and S. Furthermore, intermolecular interactions in crystal structures of 6 and 9 were determined by Hirshfeld surface (HS) analysis.