The porous crosslinked poly(vinyl alcohol) beads with the L-proline pendant was synthesized as the chiral stationary phase (CSP) for ligand-exchange chromatography of amino acid racemates via suspension polymerization of vinyl acetate and triallyl isocyanurate as a crosslinker, methanolysis of the copolymer, glycidylation of the formed crosslinked poly(vinyl alcohol), and final functionalization with L-proline. After the polymer with the chiral ligand was complexed with copper(II) cations, it was employed as the CSP to resolve the enantiomers of 15 amino acids. The results showed that the CSP possessed powerful enantioselectivity and all the tried amino acid racemates were completely separated. The large loadability (up to 60 mg per injection) permitted its application on a large scale.