The noble metal (Me = Au, Pd, Rh, and Pt) polynuclear coordination compounds of Chini’s type eventually serve as a remarkable bridge between molecular clusters and metal colloids. The sizes of the metal cores of the cluster compounds are close to lower sizes of colloidal metal particles. However, chemically stabilized nanoclusters have a distinct ligand environment with a definite stoichiometry inherent to molecular clusters. Interest in structures of the cluster compounds has increased in recent years in view of their unique selective catalytic properties under mild conditions, which, in principle, open a way to the development of a new branch of catalysis by metal clusters, quantum-size effects in the thermodynamic properties, and applications as nano-sized electronic devices (quantum dots). A key feature in structural characterization of such species (they are amorphous solids usually unsuitable for x-ray diffraction analysis) is to understand the relations between the atomic arrangement, electronic structure and chemical reactivity.