Molecular dynamics (MD) simulation was conducted to explore the extraction mechanism of Cs+ and Na+ ions in the octanol-water biphasic system containing the ionophore: dicyclohexano-18-crown-6 (DCH18C6). The rate of phase separation for the Na+NO3- system was rapid as compared to Cs+NO3- and mixed metal ion systems. Further, the binding energy during complexation of Na+ cation is -55.86 kcal/mol which was found to be more than that of Cs+ ion (-31.23 kcal/mol). A large sharp peak height for radial distribution function in both Cs-CE and Na-CE complexes suggests a high stability and a strong interaction. The self-diffusion coefficient of the Cs+-CE complex (0.054 10(-9) m(2)/s) at the octanol-water interface was found to be smaller than that of other species.