Smectites are commonly found clay mineral in temperate region soils. It exhibits variability in shrink-swell behavior and sorption of organic molecules. Previous research has established the relationship between extent of swelling and sorption of organic compounds by smectites. The effect of the interlayer cation on sorption of organic compounds and the inter-relationship between cation exchange selectivity and swelling has also been demonstrated. We investigated the effect of sorption of m-dinitrobenzene on cation exchange selectivity and the interaction between organic sorption, cation exchange, and clay swelling. We found that the adsorption of organic molecules in the interlayers of smectite influenced the affinity of the clay for inorganic cations in aqueous systems and hysteresis in cation exchange influences sorption. Sorption of m-dinitrobenzene collapsed the clay and enhanced the formation of quasicrystals. The type of cation initially saturating the clay strongly influenced the sorption, which altered the structure of quasicrystals.