(RTe)(2) (R = 2,6-dimethoxyphenyl) reacted with iodine to give [RTeTeI2R] (1), [R2TeTeR2][Te4I14] (2), and [RTe(I)I-2] (3). The synthesis of the mixed-valent, neutral complex 1 occurred easily through the reaction of (RTe)2 with mesTeI (mes = 2,4,6-trimethylphenyl), which proved the ability of mesTeI to act as a selective oxidation reagent. In the cationic species [R2TeTeR2](2+) as well in the counterion [Te4I14](2-) of compound 2, tellurium occurs in the rare oxidation state 3+.