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The design, synthesis and evaluation of chiral selectors that allow the determination of enantiomeric composition using electrospray ionization mass spectrometry are detailed herein. The enantiomers of the chiral selector were mass labeled at a distant site from the chiral recognition sites of the molecules. The mass-labeled enantiomers were mixed in a one-to-one ratio to form a quasi-racemate. Chiral recognition can be observed by comparing relative abundances of the pseudo-diastereomeric selector-analyte complexes in the mass spectrum. The observed sense of chiral recognition with mass spectrometry was consistent with that observed chromatographically using a corresponding chiral stationary phase in every case. The complex intensity fraction (CIF, intensity of one selector-analyte complex divided by the sum of the intensities for both selector-analyte complexes) is linear with the enantiomeric composition. The slope of this line is an indication of the extent of the enantioselectivity: the larger the slope, the more significant the enantioselectivity. In addition, this line can be used as a calibration curve for the quantitative determination of enantiomeric composition of the same analyte with unkown enantiomeric composition. Amide derivatives of DNB-amino acids were first used as pseudo-enantiomeric chiral selectors in the presence of added lithium chloride. The enantioselectivity values were smaller than those observed on chiral HPLC using the corresponding chiral stationary phase. The use of deprotonated DNB-amino acids as chiral selectors provides higher enantioselectivities, but with low ion abundances. Tertiary amine appended analogues of the chiral stationary phase DNB-Leucine were prepared. The amine was appended to provide a site for ready ionization (through protonation). The performance of chiral selectors of this type was compared to the original chiral selectors that lack this functional group. Chiral recognition was also observed in a reciprocal sense using proline-derived pseudo-enantiomeric chiral selectors and analytes similar to DNB-amino acid esters or amides. Optimization of the electrospray ionization conditions provided similar enantioselectivities to those from chiral HPLC. Libraries of tertiary amine appended derivatives of DNB-dipeptides, which were prepared through combinatorial peptide synthesis, were screened using electrospray ionization mass spectrometry. The use of electrospray ionization mass spectrometry as a discovery tool for new chiral selectors is discussed.