The extraction behavior of several metal ions viz., Am 3+, Eu 3+, UO22+, Th 4+, Sr 2+ and Cs + was investigated from sulphate medium employing phosphotungstic acid (PTA) and polyethylene glycol (PEG). The influence of various parameters such as pH, PTA concentration, PEG concentration and salt concentration was studied. The order of extraction followed the trend: Am3+>Eu3+>>Th4+>UOz2+>Sr2+>Cs + which deviate significantly from the reported order with conventional solvents. The relatively poor extraction of UO22+, Sr 2+ and Cs + was ascribed to their lack of interaction with the phosphotungstate anion. The separation behaviour of Am 3+ vis-a-vis Eu 3+ was also investigated under different experimental conditions.