The distribution of lanthanides and yttrium between o-xylene solutions of Adogen-464Cl and aqueous solutions of LiCl was investigated over a broad range of LiCl and extractant concentrations. It has been found that stability constants of inner sphere lantha-nide chloro complexes decrease across the series, whereas the equilibrium constants for the transfer of the negatively charged chloro complexes increase with increasing lanthanide atomic number.