Exploratory syntheses in the M-Au-Ge (M = Ca, Yb) systems have led to the discovery of two cleanly separated non-stoichiometric phases M3Au similar to 14.4Ge similar to 4.6 (I) and M3.26Au similar to 12.7Ge similar to 5.3 (II), Single crystal X-ray studies reveal that both (space group Im (3) over bar) feature body-centered-cubic packing of five-shell multiply endohedral clusters that resemble those in the parent YCd6 (= Y3Cd18) and are akin to approximate phases in other quasicrystal systems. However, differences resulting from various disorders in these are distinctive. The innermost cluster in the M3Au similar to 14.4Ge similar to 4.6 phase (I) remains a disordered tetrahedron, as in the YCd6 parent. In contrast, its counterpart in the electron-richer M3.25Au similar to 12.7Ge similar to 5.3 phase (II) is a "rattling" M atom. The structural differentiations between I and II exhibit strong correlations between lattice parameters, cluster sizes, particular site occupancies, and valence electron counts,