A highly efficient covalent immobilization procedure is considered as an essential tool for obtaining stable and reliable cyclodextrin (CD) chiral stationary phases (CSPs). This work reports the "thiolene" click immobilization of heptakis(6-mercapto-6-deoxy)-β-CD-CSP onto alkene functional silica to afford novel multiple-thioether bridged CD CSPs by controlling the surface CD concentration. Solid-state NMR, FTIR, TGA and X-ray photoelectron diffraction spectroscopy (XPS) results proved the successful preparation of the desired CSPs with different surface CD loadings. The surface CD concentrations were calculated to be 0.49 and 0.68 μmol m-2 according to the elemental analysis results. More than 60 chiral enantiomers including isoxazolines, chiral lactides, chiral ketones, dansyl amino acids, small molecule acids and alkalis as well as some flavonoids were resolved or partially separated in the reversed-phase HPLC mode. Compared with the previously prepared single thiolene bridged CD-CSP, the current multiple-thioether CD-CSP afforded much better enantioseparation ability due to the existence of the thiol moiety and a confined structure.