The synthesis of the p-sulfonate[4]calixarene (CS4)/M2+Al layered double hydroxides (Mg-Al and Zn-Al/CS4/LDHs) has been investigated as well as their adsorption behavior of benzyl alcohol (BA) in aqueous solution. The CS4/LDHs were easily synthesized by the conventional coprecipitation method. The basal spacing of the CS4/LDHs was expanded to 1.33 (Mg-Al) and 1.61 nm (Zn-Al), which indicates that CS4 cavity axis was oriented vertically (Mg-Al) and parallel (Zn-Al) to the LDH basal layer, respectively. In particular, the Zn-Al/CS4/LDH was found to have 2 types of micro pore, the CS4 cavity and the intermolecular space. The adsorption of BA to the CS4/ LDH was influenced by the amount and orientation of CS4 ion in the interlayer of the LDHs.