The trends for cation binding for several conformers of diglyme are predicted by mapping the topography of the molecular electrostatic potential (MESP) at the Hartree-Fock (HF) level. Different Li+-(diglyme) geometries derived by exploiting the MESP cooperative effects are used subsequently in ab initio computations. The binding energies for Li+ with diglyme have been calculated in mono-,,, bi- and tridentate coordinations by employing the HF, second-order Moller-Plesset (MP2) and the hybrid density functional methods. The calculated vibrational spectrum of Li+ -(diglyme) also points to a gauche conformation of diglyme in the complex.