Abstract: The reaction of a solution of Sb₂O₃ in HBr in the presence of Br₂ with a solution of 2,6-dibromopyridine (2,6-BrPy) in HBr affords supramolecular bromoantimonate polybromide (2,6-BrPy)₃[SbBr₆]-{(Br₂)Br} · 2H₂O (I). The structure of compound I is determined by X-ray structure analysis (СIF file CCDC no. 1962867). The energies of noncovalent Br···Br interactions in the solid state are estimated by quantum-chemical calculations.