The solid-state morphology of polystyrene-poly(ethylene oxide) metallo-supramolecular diblock copolymer PS20-[Ru]-PEO70, has been investigated by small-and wide-angle X-ray scattering and atomic force microscopy. Above the melting point of PEO the metal-ligand complexes and their associated counter ions are known to form aggregates within the still disordered polymer matrix of PS and PEO. Crystallization of PEO induces microphase separation between the PS and the PEO blocks. In addition, the metal-ligand aggregates are forced out of the crystalline PEO part and subsequently order at the interface in the amorphous PS block into a (short-range) square lattice. (C) 2009 Elsevier Ltd. All rights reserved.