AbstractThe tetradentate organotelluroether (C9H6NTe)2CH2 ligand has been synthesized and its coordination behaviour with a stoichiometric amount of copper(II) and silver(I) perchlorate and triflate salts has been experimentally investigated. The isolated ligand and metal complexes are characterized by multinuclear (1H, 13C, 125Te) NMR spectroscopy, single crystal X‐ray diffraction, and DFT calculations. The X‐ray analysis revealed the formation of self‐assembled bimetallic complexes with the molecular formula of 2[M(C9H6NTe)2CH2]+ X− [M+=Cu, Ag; X−=ClO4, CF3SO3]. Further, it has been noticed that the metal ions act as a bridging unit to form cationic 8‐membered metallamacrocycles in the chair conformation. The atoms in molecule (AIM) and non‐covalent interactions (NCI) analysis display a weak intramolecular Te⋅⋅⋅Te interaction. Natural bond orbital (NBO) calculations suggest that the tellurium has a rich electron donating ability toward metal ions than the quinoline nitrogen in the complexes.