Two kinds of chiral monomers, (-) α-phenylethyl-acrylamide and (-) α-phenylethyl-10-unde-cendyl amide, were synthesized via consendation of (S)-α-phenyl ethyl amine and acryl chloride or 10-unde-cendyl chloride. Their structures and purities were determined via IR, 1H NMR and elemental analysis. The seeded microspheres of polystyrene (about 3 μm) were prepared with dispersion polymerization, and monodis-perse hollow chiral polymer microspheres were prepared with two-stage swelling procedure via copolymerization of styrene, divinyl benzene and the chiral monomers synthesized above. The average diameter of the micro-sphere was about 10 μm. The chiral polymer microspheres were used to be the stationary phase of HPLC. The molar ratio of (S)-a-ethyl hydroxy phenylbutyrate and (R)-a-ethylhydroxy phenylbutyrate were determined via chiral HPLC. The chromatography results showed that the chiral recognition was very higy when using chiral polymer microsphere, prepared by S-10-undecylenoyl (a-phenyl)ethylamide as chiral monomer, as chiral stationary phase of HPLC.