Poly(piperazinyl phosphorimine) was prepared by Schotten-Boumarm method using phosphorus oxychloride and piperazine at room temperature. Polymer metal complexes were prepared in aqueous solutions using divalent metal salts viz. Cu(II), Ni(II), Mg(II), Ca(II) and Cd(II) with the polymer. Spectral evidences confirmed the formation of the metal complexes. Thermogravimetric analysis and differential scanning calorimetry were employed to investigate the thermal stability of the polymer and its metal complexes. The IR spectroscopy of the polymer and complexes suggests that metals could be co-ordinated through oxygen of the phosphorimine group and tertiary nitrogen atom. The DRS, EPR and magnetic moments confirmed the complex formation and showed the geometry of the complexes. Small angle XRD pattern shows that the polymer was amorphous, whereas the complexes were crystalline. Energy dispersive X-ray crystallographic studies confirmed the metal incorporation in the polymer chain.