The coordination of Ge-9 Zintl clusters at (carbene)Cu-I moieties is explored, and the complexes [(CAAC)Cu](2)[eta(3)-Ge-9{Si(TMS)(3)}(2)] (1), (CAAC)Cu[eta(3)-Ge-9{Si(TMS)(3)}(3)] (2), and (MIC)Cu[eta(3)-Ge-9{Si(TMS)(3)}(3)] (3) are compared with their known N-heterocyclic carbene (NHC) derivatives (A and B), where CAAC = cyclic (alkyl)amino carbene, MIC = mesoionic carbene, and TMS = trimethylsilane. In analogy to the NHC derivatives, the synthesis of 1-3 proceeds by single-step reactions of (CAAC)CuCl or (MIC)CuCl with the [Ge9R2](2-) and [Ge9R3](-) [R = Si(TMS)(3)] cluster ligands, respectively, and yields complexes of (carbene)Cu-I (carbene = CAAC, MIC) moieties exhibiting eta(3)-coordination modes of the Ge-9 deltahedron to the Cu atom. In 1, [Ge9R2](2-) acts as a eta(3)-bridging unit for two (CAAC)Cu-I moieties, and 2 and 3 feature single (carbene)Cu-I (CAAC and MIC) fragments eta(3)-connected to [Ge9R3](-) units. Analysis of the bond lengths in comparison with known examples shows a bond expansion within the coordinated Ge-3 triangular faces for all (carbene)(CuGe9)-Ge-I complexes (carbene = NHC, MIC, CAAC). All compounds are characterized by single-crystal X-ray diffractometry, NMR spectroscopy [H-1, C-13{H-1}, and Si-29{H-1}], electrospray ionization mass spectometry, elemental analysis (C, H, and N), and for the first time also by IR and Raman investigations (for 2 and 3). The new complexes add to the known NHC derivatives and extend the exploration of Ge-9 clusters with carbene ligands at Cu-I atoms.