The Cl replacement reactions of N/N or N/O spirocyclic monoferrocenylcyclotriphosphazatrienes (1-5) with the piperidine resulted in the geminal- (6-10) and tetra-piperidinophosphazenes with monoferrocenyl pendant arm (11-15). The structures of all the new compounds were determined using spectroscopic techniques. The ultrathin Langmuir-Blodgett (LB) films of two compounds (3 and 12) were prepared. The characterization of the LB films using p-polarized grazing angle (GAIR) and horizontal attenuated total reflectance (HATR) techniques was carried out. The molecular and crystal structure of the compound 6 was examined using X-ray crystallography. In addition, the interactions between six compounds (6, 7, 11, 12, 14 and 15) and pBR322 plasmid DNA were investigated by agarose gel electrophoresis.Graphical AbstractSYNOPSIS The ultrathin Langmuir-Blodgett (LB) films of two of these compounds were prepared. Molecular and crystal structure of a representative example was determined. In addition, the interactions between several of these with pBR322 plasmid DNA were investigated by agarose gel electrophoresis.