Multiple sorptive sites on natural illitic clays (e.g., frayed edge [FES], type II [TS], and planar sites [PS]) play an important role to diverse 137Cs immobilization in soil and aquifer environments. This study investigated the Cs sorption capabilities of 10 natural illitic clays at ranged Cs concentrations (1 ×10−7 to 1×10−3 mol·L−1) under various competing potassium concentration (distilled water to 1×10−1 mol·L−1). Additionally, multisite cation exchange model was performed to evaluate the best-fit sorption model and optimize the sorption capacities and affinities of multiple sorptive sites for Cs. Here, the experimental Cs sorption isotherms varied among 10 illtic clays, indicating different sorption capacities of Cs on illitic clays. The best-fit sorption model exhibited that variable Cs sorption of 10 illitic clays was significantly related to the sorption capacities at the FES (1.76 × 10−5 to 1.12×10−4 eq·kg−1), TS (1.59×10−3 to 9.76×10−3 eq·kg−1), and PS (2.14×10−2 to 1.51×10−1 eq·kg−1), respectively. The FES predominantly contributed to Cs sorption at low aqueous concentrations, whereas the TS and PS sorbed Cs at high concentrations. These sorption capabilities of multiple sorptive sites were correlated to illite contents and crystallinity of illitic clays, implicating that such parameters could be key factors to predict the Cs sorption for natural illitic clays in soil and aquifer environments. Finally, 1-D transport simulations represented that the severe Cs retardation occurred at low Cs concentration, implying that the FES predominantly affected to Cs transport in actual radioactive contamination sites (i.e., where low Cs concentration prevails), compared to the TS and/or PS.