The oxidation reaction of unsymmetrical diorganotellurides, namely, bis[2-{(dimethylamino)methyl}aryl]tellurides [aryl = phenyl (6), 2-methylphenyl (7), 2,6-dimethylphenyl (8) and 2,6-diisopropylphenyl (9)] with meta-chloroperbenzoic acid afforded the first examples of tetraorganoditelluronic acids, [RR'Te(μ-O)(OH)2]2, where R = 2-NMe2CH2C6H4, R' = C6H5 (10), 2-MeC6H4 (11), 2,6-MeC6H3 (12) and 2,6-iPrC6H3 (13). The structures of tetraorganoditelluronic acids 10-13 were authenticated by single crystal X-ray diffraction studies. From the molecular structures of 10-13, it was observed that the sp3 N-donor atoms, which were initially involved in intramolecular TeN bonding interactions in diorganotellurides 6-9, did not interact with the tellurium atoms in tetraorganoditelluronic acids 10-13. The 125Te chemical shifts for 10-13 were considerably downfield shifted as compared with the values observed for the corresponding tellurides 6-9. The relative stabilities of the tetraorganoditelluronic acids 10-13 with respect to their lighter analogues (S and Se) have been assessed using DFT calculations.