Solvent extraction has been successfully applied to metal ion preconcentration and often meant the use of toxic organic diluents. However, regulatory pressure is increasingly focusing on the use and disposal of organic solvents, and thus the development of nonhazardous alternatives is important. In this review, we examine the application of aqueous biphasic systems (ABS) to extraction of ions, analyzing their potential and limitations and suggest that ABSs could be an efficient substitute for oil/water biphasic systems. ABSs are formed by mixing certain inorganic salts and water-soluble polymers, or by mixing two water-soluble polymers.