A discrete nanospheric icosametallic cluster comprised of 20 Cu ions (1) was self-assembled from facile synthesis. Adjustment of the synthesis-by-the-choice of ligands gave rise to another cluster (2) With an intact icosacupric core and improved stability. Referring to-the synthesis of 1 and 2, a heterometallic cluster (3), which contains 12 Cu-II and 8 Zn-II was: designed and characterized by single-crystal X-ray diffraction, combined with elemental analysis, energy-dispersive X-ray, X-ray photoelectron spectroscopy, thermogravimetric analysis and element mapping. The magnetic measurements of and 3 :and the scanning electron microscopy images and diffuse-reflectance measurements of metal oxides from 2 and 3 indicate that isolation of {Cu12M8} is a new-synthetic route to materials with engineered properties.