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Diblock copolymers of poly(styrene) and poly(ethylene oxide) were prepared utilizing a bisterpyridine ruthenium complex as non‐covalent interaction for the connection of the two blocks. Apart from the synthesis and characterization of four metallo‐supramolecular block copolymers, first studies on the thermal properties of the block copolymers have been performed. A complex crystallization behavior was observed and is described in a qualitative fashion. The influence of the metal complex on the thermal stability of the metallo‐supramolecular block copolymers remains a question for further investigation.