A new silica adsorbent, C7C6CalixSi, was prepared by intermolecular hybridization. It was achieved by introducing and immobilizing a macrocyclic C7C6Calix into the pores of the hybrid silica carrier specially developed. FT-IR, SME, TG-DSC, BET, and XAR were utilized to characterize the structure of the adsorbent. C7C6Calix was successfully introduced into the macroporous silica carrier by self-assembly. The adsorption of Cs and other typical metals toward C7C6CalixSi was investigated in the range of 0.4 to 5.0 M HNO3 center dot C7C6CalixSi had an excellent adsorption ability and selectivity for Cs over others, except for Rb. The adsorption capacity of Cs was 0.1233 mM/g at the optimal adsorption conditions of 1.0 M HNO3, 298 K, and a contact time of 120 min. The experimental results fitted well with the Langmuir model. The thermodynamic parameters Delta H degrees, Delta G degrees, and Delta S degrees of Cs uptake were obtained. The stability of C7C6CalixSi was evaluated by TOC content. Some valuable adsorption data of the silica adsorbent in the chemical engineering were obtained. The results revealed that C7C6CalixSi is promising for Cs removal.