Ternary bismuth halides form an interesting functional materials class in the context of the closely related Pb halide perovsldte photovoltaics, especially given the significantly reduced toxicity of Bi when compared with Pb. The compounds A(3)Bi(2)I(9) (A = K, Rb, Cs) examined here crystallize in two different structure types: the layered defect-perovskite K3Bi2I9 type, and the Cs3Cr2CI9 type. The latter structure type features isolated Bi2I93- anions. Here, the crystal structures of the ternary iodides are redetermined and a corrected structural model for Rb3Bi2I9, as established by single crystal X-ray diffraction and solid state Rb-87 NMR spectroscopy and supported by density functional theory (DFT) calculations is presented. A variety of facile preparation techniques for single crystals, bulk materials, as well as solution-processed thin films are described. The optical properties and electronic structures are investigated experimentally by optical absorption and ultraviolet photoemission spectroscopy and computationally by DFT calculations. Absolute band positions of the valence and conduction bands of these semiconductors, with excellent agreement of experimental and calculated values, are reported, constituting a useful input for the rational interface design of efficient electronic and optoelectronic devices. The different structural connectivity in the two different structure types, somewhat surprisingly, appears to not impact band positions or band gaps in a significant manner. Computed dielectric properties, including the finding of anomalously large Born effective charge tensors on Bi3+, suggest proximal structural instabilities arising from the Be3+ 6s(2) lone pair. These anomalous Born effective charges are promising for defect screening and effective charge carrier transport. The structural, electronic, and optical properties of the complex bismuth iodides are to some extent similar to the related lead iodide perovskites. The deeper valence band positions in the complex bismuth iodides point to the need for different choices of hole transport materials for Bi-iodide based solar cell architectures.