Cation-dependent reactions “[SbBr₆]³⁻+Br₂+HBr+CationBr_x” result in the formation of bromide/polybromide complexes with zero-, one-, two-, or three-dimensional supramolecular frameworks and different Br/Sb ratios (up to 11). Seven new compounds representing six structural types were characterized by XRD and thermogravimetric analysis and DFT calculations enabled estimation of the energies of the Br⋅⋅⋅Br contacts (1.1–4.6 kcal mol⁻¹).