Reactions of TeO₂ and Br₂ in concentrated HBr in the presence of various organic cations resulted in the formation of one-dimensional supramolecular polymers with the structure cation₂{[TeBr₆](Br₂)}. In the crystal structures, the Br₂ units are connected to [TeBr₆]^2- octahedra via halogen-halogen contacts, building linear chains of two different geometries. The nature of the Br⋯Br, Br⋯Cl, and Cl⋯Cl contacts in the present and previously reported complexes of this family was investigated by theoretical methods, allowing the estimation of their energies (0.9-3.8 kcal mol^-1).