A new chiral stationary phase was designed and synthesized via surface-initiated atom-transfer radical polymerization (ATRP) and click chemistry. Poly(2-methyl-3-butyn-2-yl methacrylate-co-divinylbenzene), poly(MBMA-co-DVB), was grafted on silica surface via ATRP ("grafting-from" technique) first, and then azide-modified beta-CD was immobilized on the alkyne of the polymer layer as chiral separation material. Different crosslinking degree of poly(MBMA-co-DVB) was selected to improve the hydrophobicity of silica surface. The materials were packed into a stainless-steel column (150 mm x 4.6 mm i.d.) for high-performance liquid chromatography (HPLC), and evaluated by separation of aromatic and chiral compounds. The result demonstrated that the crosslinked benzene ring in poly(MBMA-co-DVB) can well improve the selectivity and retention time.