The metal extractant Cyanex© 272 contains bis(2,4,4-trimethylpentyl)-phosphinic acid (BTMPPA) as the main component and trioctylphosphine oxide as an impurity. As-received Cyanex 272 and pure BTMPPA were observed to significantly differ in respect to both their phase behavior during saponification and to their copper extraction ability. The differences were elucidated by investigating the effects of an addition of small amounts of tri(n-octyl)phosphine oxide (TOPO) on the phase equilibria in the system Water(2.4M NaOH)/BTMPPA/n-Hexane at 25 °C as well as in the system Water(2.4M NaOH)/BTMPPA at various temperatures. In the absence of TOPO a large microemulsion region and a small region of lyotropic liquid crystalline phase with lamellar structure are formed. When TOPO is added into the system the lamellar phase gradually disappears. The effects of TOPO on metal extraction equilibria were studied by measuring the distribution of copper(II) between a perchloric acid solution and a BTMPPA in chloroform solution in the presence and absence of tri(n-octyl)phosphine oxide.