Pyridine ligand complexes of [Bu4N][BiI4] were prepared using chelating ligands 2,2′‐bipyridyl (2,2′‐Bpy), 1,10‐phenanthroline (Phen), and 4‐nitro‐1,10‐phenanthroline (NO2Phen), producing monomeric complexes [Bu4N][(2,2′‐Bpy)BiI4], [Bu4N][(Phen)BiI4], and [Bu4N][(NO2Phen)BiI4], and bridging ligands 4,4′‐bipyridyl (4,4′‐Bpy), pyrazine (Pyz), and aminopyrazine (NH2Pyz) resulting in formation of polymers [Bu4N]n[(4,4′‐Bpy)BiI4]n and [Bu4N]2n[(RPyz)Bi2I8]n (R = H, NH2). The latter contain edge‐sharing Bi2I8 dimers. Organic ligand BiIII/CuI clusters [Bu4N]2[L2Bi2Cu2I10] {L = PPh3, P(OPh)3} and [Bu4N]2[PyBi2Cu2I10] (Py = pyridine) have been prepared. All bismuthate(III) centers are distorted octahedra and all cuprate(I) centers are tetrahedral, with organic ligands bonded to CuI. The first neutral BiI3/CuI organic ligand complex [BiCu3I6(PPh3)6] is reported. Diffuse reflectance spectroscopy measurements reveal strong absorption bands for both iodobismuthate(III) and iodocuprate(I)/bismuthate(III) complexes in the UV and visible range. Despite the similarity in absorption bands, DFT calculations support a distinct shift in transition from a mixed halide/metal‐to‐ligand charge transfer (X/MLCT) to a metal–halide cluster‐centered transition upon incorporation of copper(I) into the cluster.