Polystyrene- -polyethylene glycol (PS- -PEG) amphiphilic block copolymers featuring a terminal tridentate -ligand (terpyridine) were synthesized for the first time through an efficient route. In this approach, telechelic chain-end modified polystyrenes were produced via reversible addition-fragmentation chain-transfer (RAFT) polymerization by using terpyridine trithiocarbonate as the chain-transfer agent, after which the hydrophilic polyethylene glycol (PEG) block was incorporated into the hydrophobic polystyrene (PS) block in high yields via a thiol-ene process. Following metal-coordination with Mn , Fe , Ni , and Zn , the resulting metallo-polymers were self-assembled into spherical, vesicular nanostructures, as characterized by dynamic light scattering and transmission electron microscopy (TEM) imaging.