A novel (3-sulfopropyl methacrylate potassium)-silica hybrid monolithic column for CEC has been prepared by a simple one-pot approach based on efficient thiol-ene click chemistry. In this process, the polycondensation of hydrolyzed alkoxysilanes and in situ click reaction of vinyl groups on 3-sulfopropyl methacrylate potassium and thiol groups on the precondensed siloxanes simultaneously occurred in a pretreated capillary. Homogeneous monolithic matrix with large through-pores tightly bonded to the inner wall of the capillary was shown by optical microscope and SEM. The minimum plate height of this hybrid monolithic column was determined as 3.9 m for thiourea. Anilines, alkylbenzenes, and phenols were well separated on this hybrid monolithic column by CEC, which indicated typical reversed-phase and cation-exchange chromatographic retention mechanisms of the column.