Abstract: β-cyclodextrin polymer (β-CDP) microspheres were synthesized in inverse emulsion with β-cyclodextrin as material and epichlorohydrin as crosslinking agent. The L16（45）orthogonal test was used to obtain optimum technological parameters. The polymer microspheres were characterized by Scan electron microscope, FT-IR spectroscopy, thermogravimetric analysis (TGA) and X-ray diffraction (XRD). The results indicated that the best ratio of epichlorohydrin to β-cyclodextrin was 15∶1, the quantity of emulsifier was 1.2g, the quantity of kerosene was 60mL emulsifying temperature was 70℃ and the emulsifying time was 5h. Influence factors were emulsifying temperature, emulsifying time, the quantity of emulsifier, the ratio of epichlorohydrin to β-cyclodextrin , weight ratio of oil to water in order. The particle diameter distribution of those β-CDP microspheres under optimal conditions was relative uniform. The surface of the particles was smooth. They showed amorphous aggregate state and thermal stablity. The coating of the chromatograph was strong.