Using bentonites to adsorb aflatoxin is an effective method of minimizing the toxicity of aflatoxin to animals and humans. Early studies indicated a more than 10-fold difference in aflatoxin adsorption capacity among different bentonites. The determining mineralogical and chemical properties of the clays in aflatoxin adsorption are still poorly understood. The objective of this study was to test the hypothesis that a bentonite’s selectivity and adsorption capacity for aflatoxin is mainly determined by the ‘size matching’ requirement, on a nm scale, between the non-polar interlayer surface domains and the aflatoxin molecules. The non-polar surface domain size of smectites was varied by (1) selecting smectites with different charge densities; and (2) changing the valence and the size of exchange cations to control the amount of water in the hydration shells of the cations. Infrared spectroscopy and X-ray diffraction were also used to characterize the aflatoxin-smectite complexes to investigate if layer-charge density would affect the bonding strength between aflatoxin and the minerals. A large aflatoxin adsorption capacity and high selectivity for aflatoxin were achieved by selecting smectites that had low charge density as represented by their <110 meq/100 g cation exchange capacity. An individual smectite’s selectivity and adsorption capacity for aflatoxin could be enhanced or weakened by replacing the exchange cation. When the smectite was saturated with divalent cations that have smaller hydrated radius (