In the presence of different cations, reactions of [SbBr₆]³⁻ and I₂ result in a new family of diverse supramolecular 1D polyiodide-bromoantimonate networks. The coordination number of Sb, as well as geometry of assembling {I_x}ⁿ⁻ polyhalide units, can vary, resulting in unprecedented structural types. The nature of I⋅⋅⋅Br interactions was studied by DFT calculations; estimated energy values are 1.6–6.9 kcal mol⁻¹. Some of the compounds showed strong photoconductivity in thin films, suggesting multiple feasible applications in optoelectronics and solar energy conversion.