Reactions of Sb₂O₃ solution in HBr in presence of Br₂ with series of pyridinium-type cation salts resulted in formation of Cat[SbBr₆] (Cat = 1,3,4-MePy⁺ (1) and 1,4-MePy⁺ (2)) and Cat₂{[SbBr₆](Br₃)} (Cat = 1,2-MePy⁺ (3), 1-Et-2-MePy⁺ (4) and 1-Et-4-MePy⁺ (5)) complexes which were characterized by X-ray diffractometry. For all compounds, thermal stability was investigated by TGA method; energies of non-covalent Br⋯Br interactions were estimated by DFT calculations and QTAIM analysis (M06/DZP-DKH level of theory).