Well-defined polybutylacrylate (PBA) was prepared by atom transfer radical polymerization (ATRP). A novel end-functionalized PBA (macromolecular ligand) was synthesized via PBA bonded with thiocarbamide. Since thiocarbamide possesses strong chelating ability, end-functionalized PBA possesses some new properties such as coordination with metallic ions. After metallic ions were introduced into it, two kinds of end-functionalized PBA metal complexes were got. The structure and property of PBA, end-functionalized PBA and its metal complexes were characterized by H-1 NMR, UV, GPC, Atomic Emission Spectrometry (AES), Cyclic Voltammogram (CV) and Dielectric Constant. The results indicate that the properties of end-functionalized PBA with well-defined structure were improved greatly by introducing a small quantity of transitional metallic ions into it. The novel end-functionalized PBA metal complexes exhibit stable electrochemical activity, dielectric property and have a good prospect in many fields as functional polymer.