The adsorption of supramolecular composites for Cs(I) in high level liquid waste (HLLW) are different due to different carriers. We chose 25,27-bis(ethyl)-calix[4]arene-26,28-crown-6 (EC[4]C6) as adsorbent, SiO2-P, XAD-7 and UiO-66 as carriers. The synthesis and characterization of supramolecular EC[4]C6 loaded with three different carriers were presented. SEM, N2 adsorption/desorption isotherms, TG-DSC spectra, FT-IR spectra results shown that EC[4]C6 was successfully introduced into the pores of carriers via physical intermolecular interactions. EC[4]C6/SiO2-P, EC[4]C6/XAD-7 and EC[4]C6/UiO-66 shown high efficiency, high selectivity towards Cs(I) over 18 typical fission or corrosion products in HNO3 solution. The adsorption properties of the three materials were investigated after electron irradiation. These results demonstrate that EC[4]C6/SiO2-P possess greater potential for highly efficient removal of Cs(I) from HLLW.