Reactions of chlorotellurates(IV) and Br₂ afford formation of one-dimensional supramolecular complexes of general formula Cat₂{[TeCl₆](Br₂)} (Cat = Me₃N⁺ (1), PyH⁺ (2), 4-MePyH⁺ (3) and 1-MePy⁺ (4)) where dibromine fragments are “trapped” by [TeCl₆]³⁻via specific Br⋯Cl interactions (halogen bonding). The energies of the latter were estimated by DFT calculations (up to 5.7 kcal mol⁻¹).