Chiral stationary phase was the foundation and core of liquid chromatography. In this paper, cyclodextrin polymer (CDP) was synthesized through a simple condensation, and then bonded onto homemade silica microspheres to develop a novel chiral stationary phase. The reaction time, material ratio and reaction pathways were investigated in the process of the synthesis. And then scanning electron microscopy (SEM) was utilized to characterize its ball roundness. Blue tetrazolium method was applied to detect the content of the cyclodextrin. The result was 42.4 μmol/g, which is markedly higher than CD bonded silica gel. Finally, the product was packed with high pressure slurry method, and the chiral column was tested by liquid chromatography to separate chiral drugs. Meanwhile, the above β-CD and β-CDP were compared with ODS to resolve chiral drugs under the same chromatographic conditions. The result demonstrated that better separation was obtained by β-CDP bonded silica gel.