Extremely large separation factors (greater than 10(2)) were found for Na-Mg, K-Ca and Rb-Sr metal ion pairs on a cryptomelane-type hydrous manganese dioxide (CRYMO) ion exchanger. Ca2+ and Sr2+ ions were quantitatively separated from a thousand times of K+ and Rb+ ions on mole basis, respectively, by using the CRYMO column. The hopeful utilities of the CRYMO are suggested for the radiochemical ion-exchange separation of radiomagnesium and radiostrontium from K and Rb salt targets.