Cyanex extractants, such as Cyanex 272, Cyanex 301, and Cyanex 302 have been commercialized and widely used in the extraction and separation of metal ions in hydrometallurgy. Since Cyanex 301 and Cyanex 302 are the derivatives of Cyanex 272, these extractants have similar functional groups. In order to understand the different extraction behaviors of these extractants, an understanding of the relationship between their structure and reactivity is important. We reviewed the physicochemical properties of these extractants, such as their solubility in water, polymerization degree, acidity strength, extraction performance of metal ions, and the interaction with diluent and other extractants on the basis of their chemical structure. Synthetic methods for these extractants were also introduced. This information is of great value in the synthesis of new kinds of extractants for the extraction of metals from a diverse medium. From the literature, the extraction and stripping characteristics of metals by Cyanex 272 and its derivatives from inorganic acids such as HCl, H₂SO₄, and HNO₃ were also reviewed. The replacement of oxygen with sulfur in the functional groups (P = O to P = S group) has two opposing effects. One is to enhance their acidity and extractability due to an increase in the stability of metal complexes, and the other is to make the stripping of metals from the loaded Cyanex 301 difficult.