Herein, we report a successful resolution of L-norvaline, a racemic compound system, performed near theeutectic composition by coupling preferential crystallization with tailor-made additives. The structures ofenantiomer and racemate were characterized by PXRD, DSC, and the enantiomeric purity were measuredby Chiral HPLC. The preferential crystallization process was designed and established from binary meltingphase diagram and ternary solution phase diagram. The effects of supersaturation, solution enantiomercomposition, and seed quantity on the preferential crystallization process were investigated. However, the significant improvements of enantiomeric purity and product yield were demonstratedby additive-assisted preferential crystallization approach using tailor-made additives. These additivesbearing similar structure motifs to norvaline a highly selective binding to the racemate rather than enantiomerand remarkably suppress nucleation of DL-norvaline, the key factor determining the resultantenantiomer purity and separation efficiency. The underly inhibition principle was revealed due to thecentrosymmetric packing of the racemate while the polarity of enantiomer leads to only partial or slightcrystallization suppression. The interesting inhibition mode by tailor-made additives is also believed tobe applicable for other racemic crystallization systems. Our established additive-assisted preferentialcrystallization has showed great potential in the development of separation technology and resolutionof enantiomer from racemic compounds.