This work was designed to investigate the sorption equilibrium and kinetics of modified kaolinites of different structural order toward Cr(VI). The key reaction of modification involved an iodomethane quaternization of the mineral previously interlayer grafted with triethanolamine. This induced positively charged centers (PCNs) associated with nitrogens of ammonium salt molecules formed in the interlayer space. The positive charge was compensated by mobile iodide anions which could be ion-exchanged. Results reveal a significant increase in sorption capacity as compared to raw kaolinites and show that the sorption takes place exclusively in the interlayer space which proved to be accessible for the Cr(VI). The amount of sorbed Cr(VI) depends on the PCN content resulting from the kaolinites reactivity influenced by their structural order. An ion-exchange mechanism followed by Cr(VI) to Cr(III) reduction by iodide is proposed. The amount of initially sorbed Cr(VI) and its anionic form is strongly influenced by the pH. Desorption experiments showed that only the Cr(VI) which was not reduced (similar to 30%) was released to the solution. (C) 2013 Elsevier Inc. All rights reserved.