The reactions of (4-MeOC 6 H 4 ) 2 TeO with selected carboxylic acids and phenols afforded the formation of mononuclear organotelluroxanes. The utilization of functional carboxylic acids/phenols, such as 2,2-bis(3,5-dimethylpyrazol-1-yl)acetic acid, 2,2-bis(benzotriazole-1-yl)acetic acid, and Schiff base-containing benzoic acids and phenols allowed the preparation of organotelluroxanes containing a multi-site coordinating capability. X-ray crystal structure studies on these compounds reveal interesting supramolecular architectures in their solid-state including the presence of the four-membered Te 2 O 2 structural unit in some instances.