The extraction behavior of the ions Ni(II), Fe(III), Cd(II), Co(II), Zn(II) and Cu(II) was studied as a function of the amount of extractant added, in aqueous two-phase systems (ATPS) formed mostly by water and without the use of any organic solvent. The others ATPS components were a triblock copolymer (L35) and Na2SO4. Two types of water-soluble extractants (thiocyanate, iodide) and one slightly water-soluble extractant [1-nitroso-2-naphthol (1N2N)] were studied separately. It must be emphasized that this is the first study using a slightly water-soluble complexant for the metallic partition in ATPS, which was not a restrictive factor to the technique as believed. The extraction to the L35 rich-phase of all suited metal ions was insignificant without extractant addition. However, the effectiveness of SCN- in extracting metal ions in the system could be observed in the following sequence: Zn(II) congruent to Co(II) > Cd(II) > Cu(II) > Fe(III) > Ni(II), with Zn(II), Co(II) and Cd(II) quantitatively extracted and Cu(II) enriched by almost 80%. In the case of the l(-) extractant, all metal ions, except Cd(II) and Cu(II), remained in the salt-rich phase, providing favorable conditions to the selective separation of Ni(II), Co(II) and Fe(III) ions from Cd(II). The results show that, at pH 7.2, L35/Na2SO4/H2O ATPS can be used with 1N2N as extractant, to separate Co(II) from a complex mixture containing Fe(III), Zn(II) and Cd(II). It was observed, when using 1N2N, that a significant increase in metal extraction takes place as the pH increases, except for Cd(II) and Zn(II). (C) 2008 Elsevier B.V. All rights reserved.