Ion pair receptors based on meso-octamethylcalix[4]pyrrole (CP) have been extensively investigated over recent years. However, the nature of their ion pair recognition has barely been reported, even for CP itself. Herein, cesium chloride was used as a guest ion pair to investigate the dynamic process of ion pair recognition by CP, and the "capture-bind" mechanism for this process is proposed for the first time. The results reveal that Cs+ can be first captured by Cl- at long distances, and then it is bound to the cavity through almost equal contributions of Cl- and CP. Although the effective charge of Cl- is obviously reduced by charge-transfer, the electrostatic interactions between Cl- and Cs+ are still strong even at long distances in the presence of CP.