N-Picolyl polyurethanes (PUPY) were synthesized by nucleophilic substitution. The blends of these polyurethanes with various of transition metal chlorides [cobalt(II), nickel(II), and copper(II)] were studied by spectroscopic and thermal analysis. Ultraviolet-visible and infrared spectroscopic evidence indicates that a tetra hedral cobalt(II) complex with two pendent picolyl groups in the first-shell coordination sphere of Co2+ is formed in a series of blends with different molar ratio (from 10/1 to 2/1) of picolyl groups to cobalt(II) ions. According to the result of Small-Angle X-ray Scattering (SAXS), Differential Scanning Calorimetry(DSC), and Dynamic Mechanical Thermal Analysis (DMTA), coordination interaction between ligands in hard segments and metal ions provides a driving force for phase separation. The coordination strength of pyridine with Ni2+ is stronger than Co2+ and Cu2+.