The novel antimony tellurides have been synthesized by the electrochemically controlled cathodic dissolution of Sb2Te3 alloy electrodes. The first, [(CH3)4N]4-Sb2Te5 (1), was prepared in an ethylenediamine (en) solution of tetramethylammonium iodide and contains the novel Sb2Te54- anion, which consists of two distorted SbTe3 trigonal pyramids sharing one corner. This anion is also observed in [(C2H5)4N]4Sb2Te5 (2), which was prepared in an cn solution of tetraethylammonium iodide. Compound 3, [(C2H5)4N]4SbTe9.0.5en, which was prepared concurrently with 2, contains the unusual 15-atom cluster [Sb6Te9]4-. Shaded circles represent Te atoms in the diagrams below.