The behavior of pregabalin enantiomers obtained by resolution of the free γ-amino acid, racemic pregabalin (PGA) was investigated in the process of the resolution via diastereomeric salt formation. Various resolution methods, purification possibilities of the enantiomeric mixtures, the effect of the achiral compound, the crystallization time of the diastereomeric salt, and the effect of the solvent on the resolution were studied. Summarizing our experimental results, we can establish that the resolution of pregabalin is affected by kinetic control, and significant enantiomeric enrichment can be reached with the replenishment of the diastereomeric salt.