The association process of NaCl in aqueous solution was studied by a combination of quantum mechanical calculations on NaCl(H2O)(n) (n = 1-6) clusters and quantum mechanical/effective fragment potential-molecular dynamics (QM/EFP-MD) simulations for NaCl in 292 EFP waters. The interionic hydration structures (IHSs) were topologically classified as "ring" (R), "half-bridge" (H), and "full-bridge" (F) types on the basis of the quantum mechanical calculations. Subsequent IHS analysis on QM/EFP-MD simulations revealed that the NaCl contact ion pair (CIP) mainly involved R type hydration structures while the solvent separated ion pair (SSIP) was composed of two different groups of F-type hydration structures. Our IHS analysis also discovered H type hydration even at large separation interionic distances (similar to 7 angstrom), which is denoted as a dissociating ion pair (DIP). The analysis was able to reveal the most complete interionic structures and their reorganizations of the association process. A strong correlation between the IHSs and interionic distance suggests that not only the solvent reorganization but also the local IHS changes are equally important Mechanistically, it is suggested that the conversion between ring-type and full bridge hydration structures is the main rate determining step of ion pair association.