Zn-Al layered double hydroxides (Zn-Al LDHs) intercalated with carboxymethyl-modified cyclodextrin (CMCD) ions (CMCD center dot Zn-Al LDHs) were prepared by the co-precipitation method. The adsorption of Ni2+ by CMCD center dot Zn-Al LDHs followed the Langmuir-type mechanism, as evident from the adsorption isotherm. ESI-TOF-MS results implied that the uptake of Ni2+ by CMCD center dot Zn-Al LDHs could be attributed to the formation of chelate complexes between Ni2+ and CMCD ions in the interlayers of the CMCD center dot Zn-Al LDH. Kinetic studies revealed that the reaction involved in the uptake of Ni2+ by CMCD center dot Zn-Al LDH proceeded under mass transfer control, suggesting that the CMCD ion in the interlayer of the CMCD center dot Zn-Al LDH quickly formed a chelate complex with Ni2+. The transfer rate of Ni2+ through the product layer was rate-limiting. Similar results were obtained for the uptake of Cu2+ by CM-beta-CD center dot Zn-Al LDH. It was also found that the CM-beta-CD center dot Zn-Al LDH was more selective toward Cu2+ uptake than Ni2+ in the mixed solution. This was attributed to the Irving-Williams order of stability of bivalent transition metal complexes; Cu2+ formed a more stable chelate complex with the CM-beta-CD ion in the interlayer of CM-beta-CD center dot Zn-Al LDH as compared to Ni2+.