We present a density functional theory (DFT) based study on interaction of alkali metal cations (Li+ and Na+) with macrocyclic crown ethers of different ring sizes. The minimum energy structures, binding energies, and binding enthalpies of crown ether-cation complexes have been determined with a correlated hybrid density functional, namely Becke's three-parameter functional, B3LYP using a split valence basis function, 6-311 ++G(d, p). Geometry optimizations for all the crown ether-cation complexes were carried out with several initial guess structures based on semi-empirical PM3 optimized results. For both metal ions, the calculated values of binding energy and binding enthalpy increase with the increase in size of the crown ether ring, i.e. with the increase in the number of donor oxygen atoms in crown ether. The calculated values of gas phase binding energy for lithium ions are always higher than those for sodium ions in the case of all macrocyclic crown ethers studied at present. The calculated values of binding enthalpy are in good agreement with the reported experimental data.