Thiny black air-sensitive crystals of Bi₆₅Cu₁₃Ge ₄₁O₆Br₁₂₂ = (Bi₅) ₂(Bi₉)₆[O(GeBr₂)₃] ₆[Cu₆Ge₅Br₂₀][BiCu ₇Ge₁₈Br₆₆] were obtained by very slow cooling of a melt of bismuth, bismuth tribromide, copper, and partly oxidized germanium. The crystal structure was described in the hexagonal space group P6₃ (no. 173) with a = 2584.2(4) pm and c = 1277.4(3) pm at 296(1) K. The polarity of the structure is subtle; large parts of the structure show a pseudo mirror plane. The highly diversified structure comprises five distinct structural fragments. For the first time, two polyhedral bismuth polycations, Bi ₅³⁺ (trigonal bipyramid, D_3h) and Bi ₉⁵⁺ (tricapped trigonal prism, D_3h), occur in one and the same chemical compound. A hitherto unknown group is the C _3h-symmetric μ₃-oxido-tris[dibromidogermanate(II)] anion [O(GeBr₂)₃]^2-, in which the germanium atoms of three Ge^IIBr₂ units bind to a central oxide ion with sp² hybridization. Density-functional-theory-based calculations on an isolated [O(GeBr₂)₃]^2- anion confirm the stability of the group and its shape. Real-space chemical bonding analysis supports the polar nature of the Ge-O and Ge-Br bonds as well as the assigned oxidation states. The [O(GeBr₂)₃]^2- anion and the bismuth polycations are embedded between two kinds of one-dimensional networks, which are running parallel to the c axis, a bromido-cuprate(I)- germanate(II) network ¹_∞[Cu₆Ge ₅Br₂₀]^4- and a bromido-bismuthate(III)- cuprate(I)-germanate(II) network ¹_∞[BiCu ₇Ge₁₈Br₆₆]^20-. The latter features pentacoordinate germanium(II) atoms with bond angles close to 90°. The solution of the crystal structure from X-ray diffraction data was hampered not only by severe pseudo-symmetry and the similar scattering power of copper, germanium, and bromine atoms, but also by substantial atomic disorder and orientational disorder of the Bi₅³⁺ polycation. Bi ₆₅Cu₁₃Ge₄₁O₆Br₁₂₂ may be seen as a link between low-valent germanium compounds and low-valent bismuth compounds.