Abstract: The reactions of a solution of Sb2O3 in HBr, Br2, and 1,1'-(propane-1,3-diyl)bis(3-halogenpyridinium) bromides (halogen = Cl (I), Br (II)) afford bromoantimonates(V) Cat{[SbBr6](Br3)}, whose structures are determined by single-crystal X-Ray diffraction (SCXRD). Tribromide and hexabromoantimonate anions form supramolecular one-dimensional polymers due to the formation of a halogen bond between them, and the cations are also involved in halogen bond formation. The energies of the halogen bonds are estimated by quantum-chemical calculations.