Enantiomeric separation ability on high-performance liquid chromatography (HPLC) was compared between native and acetylated β-cyclodextrin stationary phases. In the chiral stationary phases (CSP) used in this work, β-cyclodextrin is chemically bonded to aminopropyl silica gel via sugar chain spacer. The acetylated β-cyclodextrin phase (SUMICHIRAL^TM OA-7700) exhibits excellent performance for the separation of chiral amines and amino alcohols in reversed phase mode. Conventional phosphate buffer can be used in mobile phase without special modifier and the analytical method is easy to develop. OA-7700 is very useful practically for the determination of optical purity of many important chiral amines. It can separate enantiomers of 1-phenyl-2-(p-tolyl)ethylamine (PTE) which is used for industrial scale resolution of chrysanthemic acids and norephedrin (phenylpropanolamine) which is regulated as stimulant raw material.