S-benzyl-(R)-cysteine (R-SBC) is a new chiral ligand-exchange stationary phase which has proved to be effective in the analytical separation of some natural and unnatural underivatized amino acids with fair to good separation and resolution factors. The dynamic coating of the RP-18 solid support with S-Benzyl-(R)-cysteine (R-SBC) gives rise to a stable and efficient chiral stationary phase (CSP) that has been successfully employed. The mechanism of chiral recognition is discussed and a molecular modeling study aimed at identifying molecular descriptors responsible for observed different behaviours of analytes upon different albeit closely related selectors is discussed.