Bi-2-naphthol is a kind of commonly used chiral molecule that has been widely applied in the fields of molecular recognition, materials, and asymmetric synthesis. Since there are few examples of utilizing (R)-1,1′-bi-2-naphthol derivatives used as stationary phases to resolve chiral compounds by capillary electrochromatography, three The (R)-1,1′-bi-2-naphthol derivatives were synthesized and used as stationary phases to fabricate capillary columns for chiral separation. Some of the experimental parameters for enantiomer separations were optimized. the columns exhibited good enantioselectivity for chiral alcohols, amines, ketones, and so forth. The relative standard deviation of enantiomer retention time in run-to-run, day-to-day and column-to-column experiments were 1.02, 4.45 and 5.60% using the (R)-(3,3′-di-p-cyanophenyl)-2,2′-dimethoxyl-1,1′-binaphthalene coated column, and 2.38, 3.20 and 4.94% using the (R)-(3,3′-dip-acetylphenyl)-2,2′-dimethoxy-1,1′-binaphthalene coated column. The results indicated that the (R)-1,1′-bi-2-naphthol derivatives may have utility in capillary electrochromatography.