A series of heterometallic tetranuclear complexes were developed by the reaction of a ruthenium mononuclear complex, mer-[Ru(Hbpp)(3)](2+) (Hbpp = 3,5-bis(2-pyridyl)pyrazole), with first-row transition metal ions. The obtained complexes were successfully characterized by ESI TOF-MS, elemental analysis and single crystal X-ray structural analysis. We also discussed the effect of geometrical isomerism of the precursor on the structures of the resulting heterometallic multinuclear complexes.