Non-covalent interactions between ions and πr systems play an important role in molecular recognition,catalysis and biology.To guide the screen and design for artificial hosts,catalysts and drug delivery,understanding the physical nature ofion-πr complexes via descriptors is indispensable.However,even with multiple descriptors that contain the leading term of electrostatic and polarized interactions,the quantitative description for the binding energies (BEs) ofion-π complexes is still lacking because of the intrinsic shortcomings of the commonly used descriptors.Here,we have shown that the impartment of orbital details into the electrostatic energy (coined as OEE) makes an excellent single descriptor for BEs of not only spherical,but also multiply-shaped,ion-π systems,highlighting the importance of an accurate description of the electrostatic interactions.Our results have further demonstrated that OEEs from a low-level method could be calibrated to BEs from a high-level method,offering a powerful practical strategy for an accurate prediction of a set ofion-π interactions.