The association of the electron acceptor 4,4’-amino-bipyridinium (AmV(2+)) dication and BiI(3) in an acidic solution affords three organic-inorganic hybrid materials, (AmV)(3)(BiI(6))(2) (1), (AmV)(2)(Bi(4)I(16)) (2), and (AmV)BiI(5) (3), whose structures are based on isolated BiI(6)(3-) and Bi(4)I(16)(4-) anion clusters in 1 and 2, respectively, and on a one-dimensional (1D) chain of trans-connected corner-sharing octahedra in 3. In contrast with known methylviologen-based hybrids, these compounds are more soluble in polar solvents, allowing thin film formation by spin-coating. (AmV)BiI(5) exhibits a broad absorption band in the visible region leading to an optical bandgap of 1.54 eV and shows a PV effect as demonstrated by a significant open-circuit voltage close to 500 mV. The electronic structure of the three compounds has been investigated using first-principles calculations based on density functional theory (DFT). Unexpectedly, despite the trans-connected corner-shared octahedra, for (AmV)BiI(5), the valence state shows no coupling along the wire direction, leading to a high effective mass for holes, while in contrast, the strong coupling between Bi 6p(x) orbitals in the same direction at the conduction band minimum suggests excellent electron transport properties. This contributes to the low current output leading to the low efficiency of perovskite solar cells based on (AmV)BiI(5). Further insight is provided for trans- and cis-MI(5) 1D model structures (M = Bi or Pb) based on DFT investigations.