Abstract A novel bismuthates(III) complex, (C6H14N)4[BiCl6]Cl·2H2O, was synthesized and characterized by X-ray diffraction and FT-IR spectroscopy. Its structure consists of protonated cyclohexylamine cations, discrete [BiCl6]3− anions, chlorine anions and water molecules. The chlorobismuthate(III) anions alternate with the water molecules O1 as to form hydrogen-bonded helical chain running along the crystallographic b-axis with a period of 17.622 A. These components are connected into a three-dimensional network via hydrogen bonds. In addition, the ground state geometry, vibrational wavenumbers and Natural bond orbital (NBO) analysis were studied by means of density functional theory (DFT/B3LYP) with LanL2DZ basis set. Theoretical results are within the range of the experimental data. The NBO analysis reveals the influence of the N–H…O, N–H…Cl and O H…Cl intermolecular interactions on crystal packing. Moreover, the electrochemical behavior of this complex was investigated in DMSO by cyclic voltammetry (CV).