Reactions between SnBr₂, HBr, Br₂ and bromides of different organic cations yields in formation of supramolecular bromostannate(IV) complexes where polybromide fragments are “trapped” in solid state by Br···Br noncovalent interactions. Five compounds of this family – Cat₂{[SnBr₆](Br₂)} (cat = Me₄N⁺ (1), 1-MePy⁺ (2), Me₃NH⁺ (3), 2-MePyH⁺ (4)) and (4-MePyH)₃{[SnBr₆](Br₅)} (5) – were prepared and characterized by X-ray diffractometry and Raman spectroscopy. Using DFT calculations and QTAIM analysis, we prove the existence of Br···Br noncovalent interactions in the obtained X-ray structures.