Two chiral selectors were synthesized from tartaric acid. The selectors were simultaneously immobilized on 3-aminopropyl silica gel to obtain a new biselector chiral stationary phase (CSP) in order to determine the influence of selector structure of biselector CSPs on the chiral recognition capability. For comparison, the single-selector CSP was also prepared. The biselector CSP shows an improved overall chiral recognition capability in comparison with the single-selector CSP. During the enantioseparation, temporary diastereoisomers are likely formed by complexation between a chiral analyte and the two selectors on the biselector CSP. The functional groups in the two selectors are complementary in electronic effect and/or in steric hindrance for the chiral recognition. Two selectors were synthesized from tartaric acid. The selectors were simultaneously immobilized on 3-aminopropyl silica gel to obtain a new biselector chiral stationary phase (CSP) in order to determine the influence of selector structure of bisector CSPs on the chiral recognition capability. For comparison, the single-selector CSP was also prepared. The biselector CSP shows an improved overall chiral recognition capability in comparison with the single-selector CSP. In the enantioseparation, temporary diastereoisomers are likely formed by complexation between a chiral analysis and the two selectors on the bishop CSP. The functional groups in the two selectors are complementary in electronic effect and / or in steric hindrance for the chiral recognition.