The new ditelluroethers m-C 6 H 4 (CH 2 TeMe) 2 and p-C 6 H 4 (CH 2 TeMe) 2 have been prepared in good yield from nucleophilic reaction of m- or p-C 6 H 4 (CH 2 Br) 2 and LiTeMe in THF solution. Reaction of the new ditelluroethers with MeI or I 2 affords the light yellow m- or p-C 6 H 4 (CH 2 TeMe 2 I) 2 or the red/orange m- or p-C 6 H 4 (CH 2 TeI 2 Me) 2 , respectively in high yield. These compounds have been characterised by IR, 1 H, 1 3 C{ 1 H} and 1 2 5 Te{ 1 H} NMR spectroscopy and EI mass spectrometry as appropriate. The crystal structures of the di-iodo derivatives m-C 6 H 4 (CH 2 TeI 2 Me) 2 , p-C 6 H 4 (CH 2 TeI 2 Me) 2 and the related PhI 2 Te(CH 2 ) 3 TeI 2 Ph (prepared from PhTe(CH 2 ) 3 TePh and diiodine in THF solution) are described. In each compound the TeI 2 units are axial and significant intermolecular Te...I secondary contacts (~3.6-4.1 A) are evident, which link these covalent compounds into extended networks with each Te atom in a distorted 6-coordinate environment.