Tetranuclear bromobismuthate anion [Bi ₄ Br ₁₈ ] ⁶⁻ of a brand-new structural type was found in a complex ((3,5-MePy)C ₂ ) ₃ [Bi ₄ Br ₁₈ ] (1) which was obtained by reaction of 1,1′-(ethane-1,2-diyl)bis(3,5-dimethylpyridin-1-ium) dibromide ((3,5-MePy)C ₂ Br ₂ ) with solution of Bi ₂ O ₃ in HBr. Hirshfeld surface analysis was performed for the crystal structure of 1, revealing the nature of interactions in solid state.