Cooling stochiometric mixtures of molten Bi, BiX₃, (X = Cl, Br), E (E = As, Bi), and Au yields black crystals of the low-valent, molecular compounds [Bi₁₀Au₂](EBi₃X₉) ₂. The molecules consist of an icosahedral [Bi₁₀Au ₂]⁶⁺ cluster enclosed by two (EBi₃X ₉)^3- hemi-spheres connected via Au-E bonds. The discrepancy of the symmetries of the heteroicosahedron (D_5d) and the caps (C_3v) gives rise to pseudomerohedral twinning. As a consequence of the superposition of three monoclinic unit cells (space group P2 ₁/c; e.g. a = 1059.02(5) pm, b = 1528.60(5) pm, c = 1463.55(6) pm, β = 93.69(1)° for E = Bi, X = Br), the diffraction patterns of the crystals simulate trigonal R-centered cells with lattice parameters of a ≈ 3000 pm and c ≈ 1700 pm. The constitution of the molecules can be rationalized in terms of an uncommon combination of known and new structural motives: The Wade cluster [Bi₁₀]⁴⁺ is capped by two Au⁺ atoms forming the hetero-icosahedron [Bi₁₀Au ₂]⁶⁺. In the anionic caps (E⁰Bi ^II₃X₉)^3-, the Bi^II atoms are in square planar coordination of four halogenide anions and are furthermore bonded to the E atom on the central axis of the molecule. Since the interaction between E and Au can be classified as a donor-acceptor bond, the [Au ^I(E⁰R₃)]^2- fragment with R = Bi ^IIX_2/1X_2/2 is a complex analog to cations [Au^I(E⁰R₃)]⁺ with E = P, As, Sb and R = alkyl or aryl.