Regarding HPLC chiral stationary phases, which play an important role in the development and manufacturing of pharmaceuticals, we have developed new chiral stationary phases for improved chiral separation and expanded applications. First, we designed a stationary phase in which a chiral pseudo-18-crown-6-ether derivative was covalently bonded to silica gel via an amide bond (CSP-1), this was the first product as a crown ether chemical bond type stationary phase. Next, we found that the separation performance was improved by introducing a sugar chain spacer into the cyclodextrintype stationary phase (CSP-2), and obtained remarkable chiral selectivity, especially for chiral flavones. Furthermore, we considered that chemical modification of the hydroxyl groups in cyclodextrin stationary phases significantly affects the separation ability, and showed that a stationary phase with acetylated hydroxyl groups (CSP-3) had excellent separation ability for many chiral amines. CSP-1 and CSP-3 were shown to have complementary enantioselectivity for the substituents of the guest amines, and this reason was explained by focusing on the difference in the host-guest interaction mechanism. Considering these findings, we proposed a method for selecting chiral stationary phases on the functional groups of chiral analytes.