Chiral recognition in NMR spectroscopy is achieved by converting enantiomers into distinguishable diastereomeric environments, typically through the use of chiral solvating agents. These agents interact with analytes via non-covalent forces—such as hydrogen bonding, dipole–dipole interactions, and π–π stacking—forming in situ diastereomeric complexes that generate separate NMR signals. The resulting chemical shift differences enable determination of enantiomeric excess. Significant progress has been made in developing CSAs for diverse analytes, including prochiral compounds. Common CSAs incorporate functional groups like amines, hydroxyls, carboxylic acids, or sulfoxides, and may include macrocyclic systems such as crown ethers and cyclodextrins. Effective chiral discrimination requires complementary interactions between the CSA and analyte. However, challenges such as line broadening, limited substrate compatibility, and inadequate resolution persist, motivating continued development of more efficient and broadly applicable CSAs. This chapter outlines the fundamentals of CSA-based chiral NMR recognition, highlights major CSA classes, and reviews their applications in the analysis of pharmaceutical and structurally important chiral compounds.