Liquid liquid extraction (LLE) is a process of transferring a chemical compound from one liquid phase to a second liquid phase, immiscible with the first. In LLE processes, there are many cases both in analytical and industrial chemistry where the main objective of separation is achieved by extraction using a chemical extractant. In chemical technology, the LLE of metal chelates play an important role in the purification of chemical reagents. This method is also frequently used in nuclear chemistry and technology for the separation of various radioisotopes and for the reprocessing of nuclear fuels. Zirconium/hafnium metal basically finds application in the nuclear power program due to the combination of variety of properties. It is well reported that the extractive separation of pair of metals such as zirconium and hafnium is difficult due to their similar chemical properties. LLE behavior of these metal ions with commercially available extractants such as organophosphorus, thioorganophosphorus, oximes and synthetic complexing reagents like isoxazolones is worth exploring. They could be successfully, employed for the LLE studies of tetravalent zirconium and hafnium.