The halogenation of 2,6-dibromo-9-selenabicyclo[3.3.1]-nonane 1 with 1 equivalent of molecular dihalogens (Br₂ and I₂) afforded a 1 : 1 molecular complex 1–X₂ (X = Br (2); X = I (3)), while an excess of Br₂ resulted in the ionic species [C₈H₁₂Br₂SeBr]Br₅⁻ (4). X-ray crystallographic data and the nature of Se⋯Br non-covalent bonding in the solid state and solution is discussed.