Polydichlorophosphazenes (PDCP) were synthesized from hexachlorocyclotriphosphazenes (HCCP) by ring opening polymerization (ROP) in the presence of AlCl3 as a catalyst. Poly[bis(salicylaldehyde)phosphazene](PSAP),Poly[bis (salicylaldehyde diethylamino)phospha- zene] (PBADEAP), and poly[bis(5-nitrosalicylaldehyde diethylamino) phosphazenes] (PNSADEAP) were synthesized by the macromolecular substitution of PDCP chlorines. The polymers were characterized by 1H NMR, 31P NMR and GPC. Further, self assembly behaviors of PSAP, PSADEAP and PNSADEAP were investigated in different solvents with different concentration using optical microscope and SEM techniques. Self-Assembly behavior was used for biomedical applications such as drugs delivery applications for the benefits of mankind.