Syntheses of [K([2.2.2]crypt)]+ salts of binary Pb–Bi Zintl anions and their reaction with ZnPh2 or Ni(cod)2, yielding ternary intermetalloid Ni–Pb–Bi or Zn–Pb–Bi clusters, proved the use of binary precursors with fully isoelectronic atoms as an efficient and thus valuable synthetic approach to this class of clusters. 207Pb NMR and ESI mass spectra provided insight into the solution behavior of the binary or ternary cages.