A novel and simple three-liquid-phase extraction (TLPE) approach was developed for the simultaneous removal and separation of Cr(III)) and Cr(VI)) from aqueous, solutions. The, proposed three-liquid-phase system (TLPS) consists of di(2-ethylhexyl)phosphoric acid, (D2EHPA), poly(ethylene glycol) (PEG) with a molecular Weight of 2000, and (NH4)(2)SO4. The effects of various factors including the aqueous solution pH, amounts Of (NH4)(2)SO4 and PEG, initial chromium amount, D2EHPA, concentration, phase mixing time; and diluent on the three-phase partitioning behavior of Cr(11) and Cr(VI) were evaluated, The distribution behavior of the two oxidation states of chromium was found to be highly pH-dependent. Cr(III) preferred the D2EHPA-rich top, phase through a cation exchange reaction, whereas. Cr(VI) was enriched in the PEG-rich Middle phase through : ion pair formation By appropriate selection of the extraction conditions, nearly all of the Cr(III),Was extracted into the D2EHPA top phase; and More than 90% of the Cr(VI) was transferred into the PEG rich Middle phase within 5 min. The present work highlights the possibility of Using the TLPE approach for the extraction and Separation of two different oxidation states of metal ions, such as Cr(III) and Cr(VI), in a single extraction step.