The synthesis of a hyperbranched polymer containing a rhenium bipyridine complex is seperated. The polymer was synthesized from a monomer that contains two chlorotricarbonyl rhenium (i) bipyridine moieties and a stilbazole ligand, and the polymer was formed by the coordination reaction in one single step. Gel permeation chromatography results showed that the resulting plymer had a strong interaction with the eluent was added with an electrolyte. Both atomic force microscopy and laser light scattering showed that the size of the polymer molecules was in the range between 25-30 nm. A monolayer of polymer molecules could from on a pretreated substrate by the self-assembly process, which can serve as the building block for multilayer ultrathin film devices.