a b s t r a c t The new organic–inorganic compound (C 6 H 14 N) 3 Bi 2 I 9 has been grown by the solvent evaporation method. The zero-dimensional (0-D) structure for the bismuth-iodide (C 6 H 14 N) 3 Bi 2 I 9 has been deter-mined by the single X-ray diffraction. It crystallizes at room temperature in the non-centrosymmetric space group P1c1 and consists of a cyclohexylammonium cations and a discrete (0-D) anion built up of face-sharing bioctahedra which are interconnected by means of hydrogen bonding contacts N–H⋯I. The optimized molecular structure and vibrational spectra were calculated by the Density Functional Theory (DFT) method using the B3LYP function with the LanL2DZ basis set. Good consistency is found between the calculated results and the experimental structure, IR, and Raman spectra. The detailed interpretation of the vibrational modes was carried out. Optical transmission measurements performed on thin films of (C 6 H 14 N) 3 Bi 2 I 9 revealed three absorption bands at 3.51, 2.91 and 2.46 eV. Photoluminescence measure-ments showed a peak at around 2.06 eV. The unaided-eye-detectable red luminescence emission comes from the excitonic transition in the Bi 2 I 9 anions.