||The solvent extraction of cerium(III) and samarium(III) from mixed solutions of all rare earth elements (REEs) except promethium using PC88A (2-ethyl hexyl phosphonic acid mono-2-ethyl hexyl ester), an acidic extractant, was investigated. The effects of aqueous equilibrium pH, various acids (sulfuric acid (H2 SO4 ), hydrochloric acid (HCl) and nitric acid (HNO3 )), initial metal ion concentration and extractant concentration on the solvent extraction of Ce(III) and Sm(III) were systematically studied. From the experimental results, HNO3 and HCl were found to be the preferred aqueous media for the solvent extraction of both Sm(III) and Ce(III). The most promising experimental conditions of pH, PC88A concentration and metal ion concentration were identified for the extraction of Ce(III) and Sm(III). Separation results showed that H2 SO4 at pH 2 provided the best separation between Sm(III) and Ce(III).