A bimetallic ligand-protected cluster, Ag4Ni2(DMSA)(4) (DMSA = meso-2,3-climercaptosuccinic acid) was synthesized and characterized through electrospray ionization mass spectroscopy. Such bimetallic clusters involving a noble metal and a first-row transition metal have not been previously reported. Theoretical calculations revealed an octahedral structure with silver atoms occupying the corners of the square plane and the nickel atoms at the apexes. Close agreement between the predicted and observed spectroscopic features was found.