In this paper, a novel highly cross-linked porous monolithic stationary phase having a long alkyl chain ligand (C16) was introduced and evaluated in CEC. The monolithic stationary phase was prepared by in situ copolymerization of 1-hexadecene, trimethylolpropane trimethacrylate, and 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) in the presence of ternary porogenic solvent (cydohexanol/1,4-butanediol/water). In preparing monoliths, the ternary cross-linker trimethylolpropane trimethacrylate was usually applied to preparing molecularly imprinted polymers or molecularly imprinted solid-phase extraction, instead of binary cross-linker ethylene dimethacrylate. 1-Hexadecene was introduced to provide the non-polar sites (C16) for chromatographic retention, while AMPS was used to generate the EOF for transporting the mobile phase through the monolithic capillary. Monolithic columns were prepared by optimizing proportion of porogenic solvent and AMPS content in the polymerization solution as well as the cross-linkers. The monolithic stationary phases could generate a strong and stable EOF in various pH values and exhibit an RP-chromatographic behavior for neutral compounds. For charged compounds, the separation was mainly based on the association of hydrophobic, electrostatic and electrophoretic interaction.