A rare, discrete, mixed-valent, heterometallic Fe(III)/Cu(II) cage, [Cu6Fe8L8] (ClO4)(12)center dot chi solvent (H3L = tris{[2-{(imidazole-4-yl)methylidene}amino]-ethyl}amine), was designed and synthesized via metal-ion-directed self-assembly with neutral tripodal metalloligands. The formation of this coordination cage was demonstrated by X-ray crystallography, ESI mass spectrometry, FT-IR, and UV-vis-NIR spectroscopy.