Reactions of BiI₃, I₂, and iodide salts of two different pyridinum cations result in the formation of the novel iodine-rich iodobismuthates(III) (1,3-MePy)₄{[Bi₄I₁₆](I₂)} (1) and (1-MePy){[BiI₄](I₂)_0.5) (2), where the halometalate anions are connected by diiodine linkers into one- or two-dimensional supramolecular structures. Both complexes reveal narrow optical band gaps and fairly high thermal stability, favoring their potential use in photovoltaic devices.