A series of nine bromobismuthate complexes containing Py-derived cations – (cat)₃[Bi₂Br₉] (cat = 1-i-PrPy (1), 3,5-MePyH (2), 1,2-MePy (3), 1,3-MePy (4), 1-Et-3-MePy (5), 1-Et-4-MePy (6), 1,2,4,6-MePy (7)), (2-MePyH){[BiBr₄]} (8) and (1-Bz-4-MePy)₄[Bi₂Br₁₀] (9) were prepared and characterized by X-ray diffractometry. Thermal stability was studied for synthesized compounds, as well as for the related complexes reported earlier.