Liquid-liquid extraction of the divalent metal ions manganese(H), cobah( nickel(II), copper(H), zindI1) and cadmium(I1) with 1,4,8,11-tetrathiacyclotetradecane was examined using the tetraphenylborate ion (TPB-) for the formation of the ion pairs. Copper@) was quantitatively extracted into l,Zdichloroethane, whereas the other metals were hardly extracted. The extraction behaviour of copper with 12-l&membered cyclic tetrathioethers anlaneS,, where n represents the total number of carbon and sulphur atoms in the cyclic ligand ring) was examined. Chloroform and 12-dichloroethane were used as extraction solvents. The order of the extractability of copper(U) was as follows: [lS]aneS, > [16laneS, > [14laneS, > [13]aneS, > [12laneS, at 2.5 X 10d4 M of ligands, [16laneS, > [lS]aneS, > [14]aneS, > [13laneS, > [lZ]aneS, at 2.5 x 1O-5 M of ligands. The extracted species were examined at ligand concentrations higher than 2.5 X 10e4 M. Copper was extracted with [13]aneS, and [16]aneS, as [CuLJ'+ (TPB-1, and [CuL412+ (TPB-1, d epending upon the relative concentration of the ligand to copper(U). Where L represents cyclic tetrathioethers. The extracted species with [14]aneS, and [lS]aneS, were [CuL,12'(TPB-1, and [CUL~I~+UT'B-)~, respectively. In case of [lZ]aneS,, the following three species were observed depending upon concentrations of the ligand and TPB-: [CuL,(OHPITB-, [CuL,lZ+OPB-), and [CUL~J~+(TPB-)~.