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 2 and 3 and the scanning electron microscopy images and UV-visible 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.