Supramolecular hybrid (2-ClPy)₂{[TeBr₆](Br₂)} (1) was prepared by the reaction of TeO₂, Br₂ and 2-chloropyridinium in HBr. In the structure, mononuclear [TeBr₆]²⁻ units are connected by {Br₂} linkers into 1D zigzag-shaped infinite chains. Energies of halogen bonding were estimated by theoretical methods (1.3–3.3 kcal/mol).