We have discovered the first case of enantiomeric resolution by simple recrystallization of a series of racemic crystals, although in principle this sort of enantiomeric resolution was believed to be impossible for more than a century since the mechanical resolution of enantiomeric conglomerates by Pasteur and the discovery of“Preferential Crystallization”technique by Gernetz. We have referred to this new phenomenon of enantiomeric resolution as“Preferential Enrichment”in the mother liquor. By means of X-ray crystallographic analysis and construction of the binary melting point phase diagram, it has been found that the racemic crystals of the compounds, which show Preferential Enrichment, can be classified into a highly or fairly ordered mixed crystal composed of the two enantiomers. By comparison of the presumed enantiomeric association mode in solution with the enantiomeric arrangement in the crystal, we propose a mechanism of the polymorphic transition during crystallization closely associated with Preferential Enrichment.