The supramolecular decabromide anion {Br₁₀}²⁻ was found in the structure of polybromide-bromoantimonate complex (4-MePyC₃)₂{[SbBr₆]₂{Br₁₀}} (1) (4-MePyC₃ = 1,1′(propane-1,3-diyl)bis(4-methylpyridin)-1-ium dication). {Br₁₀}²⁻ is a Z-shaped dimer of pentabromide Br₅⁻ units connected via terminal Br atoms. Each {Br₅} forms halogen bonding with one [Sb^VBr₆]⁻ anion.