A purification method is disclosed for a predetermined water-insoluble extractant present in a liquid phase composition that additionally contains one or more additional extractants, synthesis reaction starting materials, and reaction byproducts dissolved as solutes in an organic diluent. An ion-containing compound is admixed with the composition to form an extractant/ion complex in the organic diluent phase that has an affinity for a new phase that is greater than the affinity for the first-named phase. The predetermined extractant/ion complex is separated from the diluent by using the new phase affinity, and the extractant/ion complex is preferably although not necessarily recovered. The extractant/ion complex is separated into extractant and ion. The extractant is recovered. Exemplary extractants include polyethers, crown ethers, crown thioethers, calixarenes, polyamines, cryptands, porphyrins and the like.