Tetrabromoalkylthiacalix[4]arenes（1a and 1b） reacted with excess bis（tetraethylammonium）-bis（1,3- dithiole-2-thione-4,5-dithiol）zincate（2） to give thiacalix[4]arene-thiones（3a and 3b） in the presence of Na2S. Two novel bistetrathiafulvalene-attached thiacalix[4]arene assemblies（5a and 5b） formed via triethyl phosphite-mediated cross-coupling of thiacalix[4]arene-thiones（3a and 3b） and 4,5-biscyanoethylthio-1,3-dithiole-2-one（4）. All the four new compounds were characterized by 1H NMR, 13C NMR, IR, MS spectra and elemental analysis. Meanwhile, the structures of thiacalix[4]arene-thiones（3a and 3b） were identified by X-ray analysis. In addition, the cyclic voltammograms of the resulting thiacalix[4]arenes containing electroactive TTF units（5a and 5b） were provided.
