The reaction of Bi, BiCl3, and CuCl in the ionic liquid [BMIm]Cl⋅4 AlCl3 (BMIm=1‐n‐butyl‐3‐methylimidazolium) at 180 °C yielded air‐sensitive shiny black crystals of (CuBi8)[AlCl4]2[Al2Cl7] and (CuBi8)[AlCl4]3. For both compounds X‐ray diffraction on single crystals revealed monoclinic structures that contain the intermetalloid cluster (CuBi8)3+. It is the first pure bismuth cluster with a 3d metal and the first with a metal that does not form binary intermetallics with bismuth under ambient pressure. The cluster can be interpreted either as a copper(I) cation, η4‐coordinated by a square‐antiprismatic Bi82+ polycation (Bi−Cu 267 pm), or as a nine‐atomic intermetalloid nido‐cluster with 22 skeletal electrons and the C4v symmetry. One of the chloride ions of a tetrahedral [AlCl4]− group coordinates the copper atom (Cu−Cl 228 pm) and thereby completes its 18 electron count. DFT‐based calculations, followed by real‐space bonding analysis, revealed a multicenter bonding situation between copper and bismuth atoms with about seven shared electrons.