Several alkyl side chains are bonded to each polymeric repeat unit using both coordinated ligands and electrostatically bound counterions to directly control the interface curvature of the self-organized structures. 2,6-Bis(octylaminomethyl)pyridine is Zn-coordinated to poly(4-vinylpyridine) (P4VP) with dodecylbenzensulfonate (DBS) counterions, leading to multicomb polymeric supramolecules, poly[(4VP)Zn(2,6-bis(octylaminomethyl)-pyridine)(DBS)(2)]. Coordination is evidenced by infrared spectroscopy and visualized by quantum chemical calculations. The amorphous hexagonal self-organized structures are characterized using X-ray measurements.