A simple solvent extraction method has been developed for the separation of Barium from associated elements using polyether compounds. The separations are carried out from trinitrophenol medium. The adsorption of Barium was quantitative from 2M sodium acetate. It was separated from number of elements in binary mixtures. Most of the elements showed a very high tolerance limit and was possible to separate Barium from a number of elements in Multicomponent mixtures. Method is very simple, rapid, and selective and has good reproducibility.