This work investigated the morphological behavior of an acrylate-based metallo-supramolecular polymer system. RAFT (reversible addition fragmentation chain transfer) polymerization techniques were used to synthesize low molar mass, linear prepolymers of n-butyl acrylate and a 2,6-bis (1'-methylb enzimidazoly)pyridine-acrylate monomer (MeBIP-Ac) of varying concentration (2-10%). This synthesis incorporated a systematic increase of cross-link points (MeBIP ligands) pendent to the polymer backbone. A zinc(II) salt (Zn(ClO4)(2)) complexed with the pendent MeBIP ligands in a 1:2 ratio to form cross-linked polymers as free-standing films. The morphology of the neat films as well as those with added unbound MeBIP-zinc-MeBIP metal-ligand (ML) complex were characterized using transmission electron microscopy (TEM), HAADF-STEM (high angle annular dark field scanning transmission electron microscopy), energy dispersive X-ray spectroscopy (EDS), electron energy loss spectroscopy (EELS), energy-filtered TEM (EFTEM), and small-angle X-ray scattering (SAXS) techniques. A vesicle morphology in the bulk material was found for films of the neat polymer containing 2% MeBIP, while films at all other compositions exhibited a disordered microphase-separated morphology. The vesicle morphology of the 2% MeBIP films was transformed into a morphology of cylinders with the addition of unbound MeBIP-zinc-MeBIP complex.