A series of phenanthroline-functionalized phosphazene based metallo-supramolecular polymers (PFP-MSP) was synthesised using a two-step reaction strategy. In first step, three phenanthroline unit containing monomer (PFP-M) was prepared from 5,6-dihydroxy-1,10-phenanthroline and hexachlorocyclotriphosphazene by condensation reaction. Then, this PFP-M was reacted with different metal ion salts (Co, Ni, Cu, Fe, Eu, La, Tb, Lu ions) and resulting for the metallo-supramolecular polymers bearing phosphazene structure. Obtained PFP-MSPs were characterized by spectroscopic analysis, elemental analysis, Scanning electron microscopy measurement and SEM-energy dispersive X-ray spectrometry techniques. Stimuli responsible and opto-electronic properties of synthesized PFP-MSPs were also studied for different external stimulating factors, such as electrochemical or the addition of competitive complexing ligands by UV-Vis spectroscopy and electroanalytic techniques. As a result, prepared PFP-MSPs are good alternatives for photochromic, electrochromic, opto-electronic and smart material applications.