Three novel polybromotellurates(IV) were obtained by reactions of TeO₂ in conc. HBr with Br₂ and tri- or tetraalkylammonium salts. They contain [TeBr₆]^2– octahedra connected by {Br₂} linkers into one- or pseudo-two-dimensional networks. The thermal stability of the products was investigated by TGA; additionally, all compounds were characterized by Raman spectroscopy. Energies of Br···Br interactions were estimated by DFT calculations (QTAIM method).