The enantioresolution and determination of the enantiomeric purity of 24 new chiral derivatives of xanthones (CDXs) were investigated on polysaccharide-based chiral stationary phases (CSPs). The tris-3,5-dimethylphenylcarbamates of cellulose and amylose and tris-3,5-dimethoxyphenylcarbamate of amylose were selected as CSPs for this work. The separation of enantiomeric mixtures of CDXs was explored under multimodal elution conditions. All the enantiomeric mixtures of CDXs were enantioseparated with very high enantioselectivity and resolution with α and R(S) ranging from 1.43 to 12.41 and from 1.48 to 10.29, respectively. The best performances were achieved on amylose tris-3,5-dimethylphenylcarbamate stationary phase under polar organic elution conditions. Furthermore the enantiomeric purity for all the CDXs was measured, achieving values higher than 99%. Based on the obtained results, the influence of the mobile phases and structural features of the CSPs and CDXs on chiral discrimination are also discussed.