Enantiomers are essential in the pharmaceutical and food production fields owing to their distinct biological activities. In the enantiomeric separation of racemates through crystallization via diastereomeric salt formation using chiral resolving agents, salts with the same stereochemistry tend to be precipitated, regardless of the recrystallization conditions. However, the stereochemistry of the deposited salt occasionally changes, even when a homochiral resolving agent is used. Such chirality switching is an economical and time-saving technique applicable to the industrial-scale production of pure enantiomers. In this chapter, recent reports on chirality switching are reviewed. The most important trigger for the switching is solvate formation of the salt/cocrystal, which can change the stability of the diastereomeric crystals depending on the recrystallization solvent. Although prediction of solvate formation remains challenging, the problem will be overcome assisted by theoretical approach. Other factors contributing to chirality switching are also discussed based on crystal structures.