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In the title compound, C18H13Te2+·CF3O3S−, the TeII atom of the cation and one O atom of the trifluoromethanesulfonate counter-ion form a close-to-linear Te—Te—O system, with a Te—Te—O angle of 172.3 (1)° and a Te—O distance of 2.816 (5) Å, which may suggest the presence of a three-centre–four-electron (3c–4e) bond. Secondary TeO interactions [3.003 (4) and 3.016 (4) Å], involving the second TeII atom of the binuclear molecule, are also noted, resulting in a supramolecular layer in the bc plane.