Thesis includes two main parts, the first part is about the separation of the chiral dipeptides, where the enantioseparation of the LL- and DD -enantiomers of the dipeptides Ala-Phe, Ala-phenylglycine (Phg), Ala-homoPhe, Ala- β-Phe, Gly-Phe and β-Ala-Phe was studied by capillary electrophoresis in the presence of native α-, β- and γ-cyclodextrin (CD) as well as their methyl and hydroxypropyl derivatives and negatively charged CDs. Additionally, some experiments in the presence of chiral ionic liquids combination with primary chiral selectors were carried out. The synergistic effect of chiral ionic liquids composed of tetraalkylammonium ions and the amino acids Asn, Asp or Pro on the enantioseparations of dipeptides mediated by β-cyclodextrin and 2- hydroxypropyl-β-cyclodextrin in capillary electrophoresis was studied. The second part of the thesis is dedicated to the separations of the chiral sulfoxides. Sulfur as a stereogenic center can be found in synthetic compounds and natural products. The current study evaluated the enantioseparation of 16 chiral (benzylsulfinyl)benzamides compounds by capillary electrophoresis using charged cyclodextrins (CDs) as chiral selectors in 50 mM sodium acetate buffer, pH 5.5. The sulfoxides varied in the type and position of the substituent of the benzyl moiety as well as the position and methylation of the amide group. Typically, randomly substituted CDs separated the majority of the model analytes in contrast to single isomer CDs. In case of random substitution, γ-CD derivatives displayed higher resolution ability toward the set of model compounds followed by β-CD and α-CD derivatives.