The complex tetrabutylammonium(mu-tetrathiooxalato)bi [(2-thioxo-1,3-dithiole-4,5-dithiolato)cuprate(II)], (Bu(4)N)(2){tto[Cu(dmit)](2)}, is assembled using a unique and facile, three-solvent synthesis. Intrachain S ... S interactions are observed as a result of head-to-tail contacts between the thiole and thione groups of adjacent dianions. Oxidation of this complex with NaI/I-2 in acetone yields black powders with conductivities of at least 8 orders of magnitude greater than the unoxidized dianion.